Adsorbent for heteroatom species removal and uses thereof

ABSTRACT

Adsorbent materials including a porous material support and about 0.5 wt. % to about 30 wt. % of a Group 8 metal ion are provide herein. Methods of making the adsorbent material and processes of using the adsorbent material, e.g., for heteroatom species separation, are also provided herein.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Application Ser.No. 62/091,071 filed Dec. 12, 2014 and U.S. Provisional Application Ser.No. 62/091,077 filed Dec. 12, 2014, which are herein incorporated byreference in their entirety.

This application is also related to several other co-pending U.S.applications, filed on even date herewith and bearing Attorney DocketNos. 2014EM304-US2 (entitled “Organosilica Materials and Uses Thereof”),2014EM305-US2 (entitled “Methods of Producing Organosilica Materials andUses Thereof”), 2015EM382 (entitled “Aromatic Hydrogenation Catalystsand Uses Thereof”), 2015EM383 (entitled “Organosilica Materials and UsesThereof”), 2015EM384 (entitled “Organosilica Materials and UsesThereof”), 2015EM385 (entitled “Organosilica Materials and UsesThereof”), 2015EM386 (entitled “Organosilica Materials and UsesThereof”), 2015EM387 (entitled “Coating Method Using OrganosilicaMaterials and Uses Thereof”), 2015EM388 (entitled “Membrane FabricationMethod Using Organosilica Materials and Uses Thereof”), and 2015EM390(entitled “Method for Separating Aromatic Compounds from LubeBasestocks”), the entire disclosures of each of which are incorporatedby reference herein.

Additionally, this application is further related to several otherco-pending U.S. applications, filed on even date herewith and bearingAttorney Docket Nos. 2015EM375 (entitled “Organosilica Materials for Useas Adsorbents for Oxygenate Removal”), 2015EM376 (entitled “SupportedCatalyst for Olefin Polymerization”), 2015EM377 (entitled “SupportedCatalyst for Olefin Polymerization”), 2015EM378 (entitled “SupportedCatalyst for Olefin Polymerization”), and 2015EM379 (entitled “SupportedCatalyst for Olefin Polymerization”), the entire disclosures of each ofwhich are incorporated by reference herein.

FIELD OF THE INVENTION

This invention relates to an adsorbent and use of the adsorbent forheteroatom species removal from a hydrocarbon feedstream.

BACKGROUND OF THE INVENTION

Typically, any number of petrochemical feeds, such as whole crude, lightgas oil (LGO), light cycle oil (LCO) and virgin diesel, require removalof heteroatom species. Such heteroatom species includenitrogen-containing and/or sulfur-containing species. For example,hydrotreating is used to lower content of nitrogen-containing and/or orsulfur-containing species from petrochemical feeds (e.g., virgindiesel). However, nitrogen-containing species can poison thehydrotreating catalysts. Thus, high pressure hydrotreating is necessaryto overcome nitrogen poisoning of the catalysts and to effectivelyremove the sulfur-containing species to meet sulfur contentspecifications of the various feedstreams. Thus, there is a need for anadsorbent which can remove or separate nitrogen-containing species frompetrochemical feeds prior to hydrotreating so that hydrotreating may beperformed at lower pressures.

Porous inorganic solids have found great utility as separation media forindustrial application. In particular, mesoporous materials, such assilicas and aluminas, having a periodic arrangement of mesopores areattractive materials for use in adsorption and separation processes dueto their uniform and tunable pores, high surface areas and large porevolumes. Such mesoporous materials are known to have large specificsurface areas (e.g., 1000 m²/g) and large pore volumes (e.g., 1 cm³/g).For these reasons, such mesoporous materials enable molecules to rapidlydiffuse into the pores and therefore, can be advantageous over zeolites,which have smaller pore sizes. Consequently, such mesoporous materialscan be useful as large capacity adsorbents.

However, mesoporous organosilicas, which may be used as adsorbents areconventionally formed by the self-assembly of the silsequioxaneprecursor in the presence of a structure directing agent, a porogenand/or a framework element. The precursor is hydrolysable and condensesaround the structure directing agent. These materials have been referredto as Periodic Mesoporous Organosilicates (PMOs), due to the presence ofperiodic arrays of parallel aligned mesoscale channels. For example,Landskron, K., et al. [Science, 302:266-269 (2003)] report theself-assembly of 1,3,5-tris[diethoxysila]cylcohexane [(EtO)₂SiCH₂]₃ inthe presence of a base and the structure directing agent,cetyltrimethylammonium bromide to form PMOs that are bridgedorganosilicas with a periodic mesoporous framework, which consist ofSiO₃R or SiO₂R₂ building blocks, where R is a bridging organic group. InPMOs, the organic groups can be homogenously distributed in the porewalls. U.S. Pat. Pub. No. 2012/0059181 reports the preparation of acrystalline hybrid organic-inorganic silicate formed from 1,1,3,3,5,5hexaethoxy-1,3,5 trisilyl cyclohexane in the presence of NaAlO₂ andbase. U.S. Patent Application Publication No. 2007/003492 reportspreparation of a composition formed from 1,1,3,3,5,5 hexaethoxy-1,3,5trisilyl cyclohexane in the presence of propylene glycol monomethylether.

However, the use of a structure directing agent, such as a surfactant,in the preparation of an organosilica material, requires a complicated,energy intensive process to eliminate the structure directing agent atthe end of the preparation process. For example, calcining may berequired as well as wastewater disposal steps and associated costs todispose of the structure directing agent. This limits the ability toscale-up the process for industrial applications.

Therefore, there is a need for improved adsorbents and/or processes forheteroatom species removal or separation from hydrocarbon feeds usingorganosilica materials that can be prepared by a method that can bepracticed in the absence of a structure directing agent, a porogen orsurfactant.

SUMMARY OF THE INVENTION

It has been found that adsorbents comprising organosilica material withdesirable pore diameter, pore volume, and surface area can be achieved.Further, such adsorbents can be successfully prepared without the needfor a structure directing agent, a porogen or surfactant.

Thus, in one aspect, embodiments of the invention provide an adsorbentmaterial comprising: a porous material support; and about 0.5 wt % toabout 30 wt % of a Group 8 metal ion.

In still another aspect, embodiments of the invention provide a methodof making an adsorbent material, the method comprising: (a) impregnatinga porous material support with an aqueous solution of a Group 8 metalion, wherein the porous material comprises between about 0.5 wt % toabout 30 wt % of the Group 8 metal ion; and (b) drying the impregnatedporous material support.

In still another aspect, embodiments of the invention provide a methodof separating a heteroatom species from a hydrocarbon feedstream, themethod comprising contacting the hydrocarbon feedstream containing atleast one heteroatom species with the adsorbent material describedherein.

Other embodiments, including particular aspects of the embodimentssummarized above, will be evident from the detailed description thatfollows.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates nitrogen removal (total remaining in ppm) from virgindiesel using the following materials: Ground Up Davisil 646, Ball-MilledDavisil 646 w/ 3% Fe³⁺, Ball-Milled Davisil 646 w/ 6% Fe³⁺ andBall-Milled Davisil 646 w/ 10% Fe³⁺.

FIG. 2 illustrates nitrogen removal (% remaining) from virgin dieselusing the following materials: Ground Up Davisil 646, Ball-MilledDavisil 646 w/ 3% Fe³⁺, Ball-Milled Davisil 646 w/ 6% Fe³⁺ andBall-Milled Davisil 646 w/10% Fe³⁺.

FIG. 3 illustrates nitrogen removal (total remaining in ppm) from virgindiesel using the following materials: Ground Up Davisil 646, Ball-MilledDavisil 646 w/ 3% Fe³⁺, Ball-Milled Davisil 646 w/ 10% Fe³⁺, ComparativeTEOS-MO, Comparative MO (1^(st)-3^(rd) runs), Cu²⁺-TEOS-MO andFe³⁺-TEOS-MO.

FIG. 4 illustrates nitrogen removal (% remaining) from virgin dieselusing the following materials: Ground Up Davisil 646, Ball-MilledDavisil 646 w/ 3% Fe³⁺, Ball-Milled Davisil 646 w/ 10% Fe³⁺, ComparativeTEOS-MO, Comparative MO (1^(st)-3^(rd) runs), Cu²⁺-TEOS-MO andFe³⁺-TEOS-MO.

FIG. 5 illustrates nitrogen removal (total remaining in ppm) from virgindiesel using the following materials: Ground Up Davisil 646, Ball-MilledDavisil 646 w/ 3% Fe³⁺, Ball-Milled Davisil 646 w/ 10% Fe³⁺, ComparativeTEOS-MO, Comparative MO (1^(st)-3^(rd) runs), Cu²⁺-TEOS-MO,Fe³⁺-TEOS-MO, N₂ Calcined MCM-41A, N₂ Calcined MCM-41B, N₂ CalcinedMCM-41C, N₂ Calcined MCM-41D, Air Calcined MCM-41A, Air CalcinedMCM-41B, Air Calcined MCM-41C and Air Calcined MCM-41D.

FIG. 6 illustrates nitrogen removal (% remaining) from virgin dieselusing the following materials: Ground Up Davisil 646, Ball-MilledDavisil 646 w/ 3% Fe³⁺, Ball-Milled Davisil 646 w/ 10% Fe³⁺, ComparativeTEOS-MO, Comparative MO (1^(st)-3^(rd) runs), Cu²⁺-TEOS-MO,Fe³⁺-TEOS-MO, N₂ Calcined MCM-41A, N₂ Calcined MCM-41B, N₂ CalcinedMCM-41C, N₂ Calcined MCM-41D, Air Calcined MCM-41A, Air CalcinedMCM-41B, Air Calcined MCM-41C and Air Calcined MCM-41D.

FIG. 7 illustrates sulfur removal (total content wt. %) from virgindiesel using the following materials: Comparative MO (1^(st) run), N₂Calcined MCM-41A, N₂ Calcined MCM-41B, N₂ Calcined MCM-41C, N₂ CalcinedMCM-41D, Air Calcined MCM-41A, Air Calcined MCM-41B, Air CalcinedMCM-41C and Air Calcined MCM-41D.

FIG. 8 illustrates sulfur removal (% remaining) from virgin diesel usingthe following materials: Comparative MO (1^(st) run), N₂ CalcinedMCM-41A, N₂ Calcined MCM-41B, N₂ Calcined MCM-41C, N₂ Calcined MCM-41D,Air Calcined MCM-41A, Air Calcined MCM-41B, Air Calcined MCM-41C and AirCalcined MCM-41D.

FIG. 9 illustrates nitrogen removal (total remaining in ppm) from Fawleylight gas oil (LGO) using the following materials: Ball Milled Davisil646, Ball Milled Davisil 635, Davisil 635 w/ 1% Fe³⁺, Davisil 646 w/ 1%Fe³⁺, Davisil 646 w/ 3% Fe³⁺, Davisil 646 w/ 6% Fe³⁺ and Davisil 646 w/10% Fe³⁺.

FIG. 10 illustrates nitrogen removal (% remaining) from Fawley LGO usingthe following materials: Ball Milled Davisil 646, Ball Milled Davisil635, Davisil 635 w/ 1% Fe³⁺, Davisil 646 w/ 1% Fe³⁺, Davisil 646 w/ 3%Fe³⁺, Davisil 646 w/ 6% Fe³⁺ and Davisil 646 w/ 10% Fe³⁺.

FIG. 11 illustrates nitrogen removal (total remaining in ppm) fromFawley LGO using the following materials: Ball Milled Davisil 646, BallMilled Davisil 635, Davisil 646 w/ 3% Fe³⁺, Fe³⁺-TEOS-MO, Norit RX-3 andSorbonit-4.

FIG. 12 illustrates nitrogen removal (% remaining) from Fawley LGO usingthe following materials: Ball Milled Davisil 646, Ball Milled Davisil635, Davisil 646 w/ 3% Fe³⁺, Fe³⁺-TEOS-MO, Norit RX-3 and Sorbonit-4.

FIG. 13 illustrates nitrogen removal (total remaining in ppm) fromFawley light cycle oil (LCO) using the following materials: Ball MilledDavisil 646, Ball Milled Davisil 646 w/ 1% Fe³⁺, Ball Milled Davisil 646w/ 3% Fe³⁺, Ball Milled Davisil 646 w/ 6% Fe³⁺ and Ball Milled Davisil646 w/ 10% Fe³⁺.

FIG. 14 illustrates nitrogen removal (% remaining) from Fawley LCO usingthe following materials: Ball Milled Davisil 646, Ball Milled Davisil646 w/ 1% Fe³⁺, Ball Milled Davisil 646 w/ 3% Fe³⁺, Ball Milled Davisil646 w/ 6% Fe³⁺ and Ball Milled Davisil 646 w/ 10% Fe³⁺.

FIG. 15 illustrates nitrogen removal (total remaining in ppm) fromFawley LCO using the following materials: Ball Milled Davisil 646, BallMilled Davisil 646 w/ 3% Fe³⁺ and Fe³⁺-TEOS-MO.

FIG. 16 illustrates nitrogen removal (% remaining) from Fawley LCO usingthe following materials: Ball Milled Davisil 646, Ball Milled Davisil646 w/ 3% Fe³⁺ and Fe³⁺-TEOS-MO.

FIG. 17 illustrates nitrogen removal (total remaining in ppm) fromJoliet LCO using the following materials: Davisil 646, Davisil 646 w/ 1%Fe³⁺, Davisil 646 w/ 3% Fe³⁺ and Evonik 4210 w/ 6% Fe³⁺.

FIG. 18 illustrates nitrogen removal (% remaining) from Joliet LCO usingthe following materials: Davisil 646, Davisil 646 w/ 1% Fe³⁺, Davisil646 w/ 3% Fe³⁺ and Evonik 4210 w/ 6% Fe³⁺.

FIG. 19 illustrates nitrogen removal (total remaining in ppm) fromJoliet LCO using the following materials: Davisil 646, Davisil 646 w/ 3%Fe³⁺ and Fe³⁺-TEOS-MO.

FIG. 20 illustrates nitrogen removal (% remaining) from Joliet LCO usingthe following materials: Davisil 646, Davisil 646 w/ 3% Fe³⁺ andFe³⁺-TEOS-MO.

FIG. 21 illustrates nitrogen removal (total remaining in ppm) from ChibaLCO using the following materials: Davisil 635 w/ 1% Fe³⁺ andFe³⁺-TEOS-MO.

FIG. 22 illustrates nitrogen removal (% remaining) from Chiba LCO usingthe following materials: Davisil 635 w/ 1% Fe³⁺ and Fe³⁺-TEOS-MO.

FIG. 23 illustrates nitrogen removal (total remaining in ppm) fromArabian Extra Light Crude using the following materials: Davisil 646 w/3% Fe³⁺ and Davisil 646 w/ 6% Fe³⁺.

FIG. 24 illustrates nitrogen removal (% remaining) from Arabian ExtraLight Crude using the following materials: Davisil 646 w/ 3% Fe³⁺ andDavisil 646 w/ 6% Fe³⁺.

FIG. 25 illustrates nitrogen removal (total remaining in ppm) fromArabian Extra Light Crude using the following materials: Davisil 646 w/3% Fe³⁺, Comparative MO and Fe³⁺-TEOS-MO.

FIG. 26 illustrates nitrogen removal (% remaining) from Arabian ExtraLight Crude using the following materials: Davisil 646 w/ 3% Fe³⁺,Comparative MO and Fe³⁺-TEOS-MO.

DETAILED DESCRIPTION OF THE INVENTION

In various aspects of the invention, hydrogenation catalysts, methodsfor preparing hydrogenation catalysts and aromatics hydrogenationprocesses are provided.

I. DEFINITIONS

For purposes of this invention and the claims hereto, the numberingscheme for the Periodic Table Groups is according to the IUPAC PeriodicTable of Elements.

The term “and/or” as used in a phrase such as “A and/or B” herein isintended to include “A and B”, “A or B”, “A”, and “B”.

The terms “substituent”, “radical”, “group”, and “moiety” may be usedinterchangeably.

As used herein, and unless otherwise specified, the term “C_(n)” meanshydrocarbon(s) having n carbon atom(s) per molecule, wherein n is apositive integer.

As used herein, and unless otherwise specified, the term “hydrocarbon”means a class of compounds containing hydrogen bound to carbon, andencompasses (i) saturated hydrocarbon compounds, (ii) unsaturatedhydrocarbon compounds, and (iii) mixtures of hydrocarbon compounds(saturated and/or unsaturated), including mixtures of hydrocarboncompounds having different values of n.

As used herein, and unless otherwise specified, the term “alkyl” refersto a saturated hydrocarbon radical having from 1 to 12 carbon atoms(i.e. C₁-C₁₂ alkyl), particularly from 1 to 8 carbon atoms (i.e. C₁-C₈alkyl), particularly from 1 to 6 carbon atoms (i.e. C₁-C₆ alkyl), andparticularly from 1 to 4 carbon atoms (i.e. C₁-C₄ alkyl). Examples ofalkyl groups include, but are not limited to, methyl, ethyl, propyl,butyl, pentyl, hexyl, heptyl, octyl, decyl, and so forth. The alkylgroup may be linear, branched or cyclic. “Alkyl” is intended to embraceall structural isomeric forms of an alkyl group. For example, as usedherein, propyl encompasses both n-propyl and isopropyl; butylencompasses n-butyl, sec-butyl, isobutyl and tert-butyl and so forth. Asused herein, “C₁ alkyl” refers to methyl (—CH₃), “C₂ alkyl” refers toethyl (—CH₂CH₃), “C₃ alkyl” refers to propyl (—CH₂CH₂CH₃) and “C₄ alkyl”refers to butyl (e.g. —CH₂CH₂CH₂CH₃, —(CH₃)CHCH₂CH₃, —CH₂CH(CH₃)₂,etc.). Further, as used herein, “Me” refers to methyl, and “Et” refersto ethyl, “i-Pr” refers to isopropyl, “t-Bu” refers to tert-butyl, and“Np” refers to neopentyl.

As used herein, and unless otherwise specified, the term “alkylene”refers to a divalent alkyl moiety containing 1 to 12 carbon atoms (i.e.C₁-C₁₂ alkylene) in length and meaning the alkylene moiety is attachedto the rest of the molecule at both ends of the alkyl unit. For example,alkylenes include, but are not limited to, —CH₂—, —CH₂CH₂—,—CH(CH₃)CH₂—, —CH₂CH₂CH₂—, etc. The alkylene group may be linear orbranched.

As used herein, and unless otherwise specified, the term“nitrogen-containing alkyl” refers to an alkyl group as defined hereinwherein one or more carbon atoms in the alkyl group is substituted witha nitrogen atom or a nitrogen-containing cyclic hydrocarbon having from2 to 10 carbon atoms (i.e., a nitrogen-containing cyclic C₂-C₁₀hydrocarbon), particularly having from 2 to 5 carbon atoms (i.e., anitrogen-containing cyclic C₂-C₅ hydrocarbon), and particularly havingfrom 2 to 5 carbon atoms (i.e., a nitrogen-containing cyclic C₂-C₅hydrocarbon). The nitrogen-containing cyclic hydrocarbon may have one ormore nitrogen atoms. The nitrogen atom(s) may optionally be substitutedwith one or two C₁-C₆ alkyl groups. The nitrogen-containing alkyl canhave from 1 to 12 carbon atoms (i.e. C₁-C₁₂ nitrogen-containing alkyl),particularly from 1 to 10 carbon atoms (i.e. C₁-C₁₀ nitrogen-containingalkyl), particularly from 2 to 10 carbon atoms (i.e. C₂-C₁₀nitrogen-containing alkyl), particularly from 3 to 10 carbon atoms (i.e.C₃-C₁₀ nitrogen-containing alkyl), and particularly from 3 to 8 carbonatoms (i.e. C₁-C₁₀ nitrogen-containing alkyl). Examples ofnitrogen-containing alkyls include, but are not limited to,

As used herein, and unless otherwise specified, the term“nitrogen-containing alkylene” refers to an alkylene group as definedherein wherein one or more carbon atoms in the alkyl group issubstituted with a nitrogen atom. The nitrogen atom(s) may optionally besubstituted with one or two C₁-C₆ alkyl groups. The nitrogen-containingalkylene can have from 1 to 12 carbon atoms (i.e. C₁-C₁₂nitrogen-containing alkylene), particularly from 2 to 10 carbon atoms(i.e. C₂-C₁₀ nitrogen-containing alkylene), particularly from 3 to 10carbon atoms (i.e. C₃-C₁₀ nitrogen-containing alkylene), particularlyfrom 4 to 10 carbon atoms (i.e. C₄-C₁₀ nitrogen-containing alkylene),and particularly from 3 to 8 carbon atoms (i.e. C₃-C₈nitrogen-containing alkyl). Examples of nitrogen-containing alkylenesinclude, but are not limited to,

As used herein, and unless otherwise specified, the term “alkenyl”refers to an unsaturated hydrocarbon radical having from 2 to 12 carbonatoms (i.e., C₂-C₁₂ alkenyl), particularly from 2 to 8 carbon atoms(i.e., C₂-C₈ alkenyl), particularly from 2 to 6 carbon atoms (i.e.,C₂-C₆ alkenyl), and having one or more (e.g., 2, 3, etc.) carbon-carbondouble bonds. The alkenyl group may be linear, branched or cyclic.Examples of alkenyls include, but are not limited to ethenyl (vinyl),2-propenyl, 3-propenyl, 1,4-pentadienyl, 1,4-butadienyl, 1-butenyl,2-butenyl and 3-butenyl. “Alkenyl” is intended to embrace all structuralisomeric forms of an alkenyl. For example, butenyl encompasses1,4-butadienyl, 1-butenyl, 2-butenyl and 3-butenyl, etc.

As used herein, and unless otherwise specified, the term “alkenylene”refers to a divalent alkenyl moiety containing 2 to about 12 carbonatoms (i.e. C₂-C₁₂ alkenylene) in length and meaning that the alkylenemoiety is attached to the rest of the molecule at both ends of the alkylunit. For example, alkenylenes include, but are not limited to, —CH═CH—,—CH═CHCH₂—, —CH═CH═CH—, —CH₂CH₂CH═CHCH₂—, etc. —CH₂CH₂—, —CH(CH₃)CH₂—,—CH₂CH₂CH₂—, etc. The alkenylene group may be linear or branched.

As used herein, and unless otherwise specified, the term “alkynyl”refers to an unsaturated hydrocarbon radical having from 2 to 12 carbonatoms (i.e., C₂-C₁₂ alkynyl), particularly from 2 to 8 carbon atoms(i.e., C₂-C₈ alkynyl), particularly from 2 to 6 carbon atoms (i.e.,C₂-C₆ alkynyl), and having one or more (e.g., 2, 3, etc.) carbon-carbontriple bonds. The alkynyl group may be linear, branched or cyclic.Examples of alkynyls include, but are not limited to ethynyl,1-propynyl, 2-butynyl, and 1,3-butadiynyl. “Alkynyl” is intended toembrace all structural isomeric forms of an alkynyl. For example,butynyl encompasses 2-butynyl, and 1,3-butadiynyl and propynylencompasses 1-propynyl and 2-propynyl (propargyl).

As used herein, and unless otherwise specified, the term “alkynylene”refers to a divalent alkynyl moiety containing 2 to about 12 carbonatoms (i.e. C₂-C₁₂ alkenylene) in length and meaning that the alkylenemoiety is attached to the rest of the molecule at both ends of the alkylunit. For example, alkenylenes include, but are not limited to, —C≡C—,—C≡CCH₂—, —C≡CCH₂C≡C—, —CH₂CH₂C≡CCH₂—, etc. —CH₂CH₂—, —CH(CH₃)CH₂—,—CH₂CH₂CH₂—, etc. The alkylene group may be linear or branched.

As used herein, and unless otherwise specified, the term “alkoxy” refersto —O-alkyl containing from 1 to about 10 carbon atoms. The alkoxy maybe straight-chain or branched-chain. Non-limiting examples includemethoxy, ethoxy, propoxy, butoxy, isobutoxy, tert-butoxy, pentoxy, andhexoxy. “C₁ alkoxy” refers to methoxy, “C₂ alkoxy” refers to ethoxy, “C₃alkoxy” refers to propoxy and “C₄ alkoxy” refers to butoxy. Further, asused herein, “OMe” refers to methoxy and “OEt” refers to ethoxy.

As used herein, and unless otherwise specified, the term “aromatic”refers to unsaturated cyclic hydrocarbons having a delocalizedconjugated π system and having from 5 to 20 carbon atoms (aromaticC₅-C₂₀ hydrocarbon), particularly from 5 to 12 carbon atoms (aromaticC₅-C₁₂ hydrocarbon), and particularly from 5 to 10 carbon atoms(aromatic C₅-C₁₂ hydrocarbon). Exemplary aromatics include, but are notlimited to benzene, toluene, xylenes, mesitylene, ethylbenzenes, cumene,naphthalene, methylnaphthalene, dimethylnaphthalenes, ethylnaphthalenes,acenaphthalene, anthracene, phenanthrene, tetraphene, naphthacene,benzanthracenes, fluoranthrene, pyrene, chrysene, triphenylene, and thelike, and combinations thereof. Additionally, the aromatic may compriseone or more heteroatoms. Examples of heteroatoms include, but are notlimited to, nitrogen, oxygen, and/or sulfur. Aromatics with one or moreheteroatom include, but are not limited to furan, benzofuran, thiophene,benzothiophene, oxazole, thiazole and the like, and combinationsthereof. The aromatic may comprise monocyclic, bicyclic, tricyclic,and/or polycyclic rings (in some embodiments, at least monocyclic rings,only monocyclic and bicyclic rings, or only monocyclic rings) and may befused rings.

As used herein, and unless otherwise specified, the term “aryl” refersto any monocyclic or polycyclic cyclized carbon radical containing 6 to14 carbon ring atoms, wherein at least one ring is an aromatichydrocarbon. Examples of aryls include, but are not limited to phenyl,naphthyl, pyridinyl, and indolyl.

As used herein, and unless otherwise specified, the term “aralkyl”refers to an alkyl group substituted with an aryl group. The alkyl groupmay be a C₁-C₁₀ alkyl group, particularly a C₁-C₆, particularly a C₁-C₄alkyl group, and particularly a C₁-C₃ alkyl group. Examples of aralkylgroups include, but are not limited to phenylmethyl, phenylethyl, andnaphthylmethyl. The aralkyl may comprise one or more heteroatoms and bereferred to as a “heteroaralkyl.” Examples of heteroatoms include, butare not limited to, nitrogen (i.e., nitrogen-containing heteroaralkyl),oxygen (i.e., oxygen-containing heteroaralkyl), and/or sulfur (i.e.,sulfur-containing heteroaralkyl). Examples of heteroaralkyl groupsinclude, but are not limited to, pyridinylethyl, indolylmethyl,furylethyl, and quinolinylpropyl.

As used herein, and unless otherwise specified, the term “heterocyclo”refers to fully saturated, partially saturated or unsaturated orpolycyclic cyclized carbon radical containing from 4 to 20 carbon ringatoms and containing one or more heteroatoms atoms. Examples ofheteroatoms include, but are not limited to, nitrogen (i.e.,nitrogen-containing heterocyclo), oxygen (i.e., oxygen-containingheterocyclo), and/or sulfur (i.e., sulfur-containing heterocyclo).Examples of heterocyclo groups include, but are not limited to, thienyl,furyl, pyrrolyl, piperazinyl, pyridyl, benzoxazolyl, quinolinyl,imidazolyl, pyrrolidinyl, and piperidinyl.

As used herein, and unless otherwise specified, the term“heterocycloalkyl” refers to an alkyl group substituted with heterocyclogroup. The alkyl group may be a C₁-C₁₀ alkyl group, particularly aC₁-C₆, particularly a C₁-C₄ alkyl group, and particularly a C₁-C₃ alkylgroup. Examples of heterocycloalkyl groups include, but are not limitedto thienylmethyl, furylethyl, pyrrolylmethyl, piperazinylethyl,pyridylmethyl, benzoxazolylethyl, quinolinylpropyl, andimidazolylpropyl.

As used herein, the term “heteroatom” refers to atoms other thanhydrogen or carbon. Examples of heteroatoms include, but are not limitedto, nitrogen, oxygen, halogens, phosphorus, and sulfur.

As used herein, the term “hydroxyl” refers to an —OH group.

As used herein, the term “mesoporous” refers to solid materials havingpores that have a diameter within the range of from about 2 nm to about50 nm.

As used herein, the term “organosilica” refers to an organosiloxanecompound that comprises one or more organic groups bound to two or moreSi atoms.

As used herein, the term “siliceous” refers to any material containingsilica (SiO₂) and/or silicate.

As used herein, the term “silanol” refers to a Si—OH group.

As used herein, the term “silanol content” refers to the percent of theSi—OH groups in a compound and can be calculated by standard methods,such as NMR.

As used herein, the terms “structure directing agent,” “SDA,” and/or“porogen” refer to one or more compounds added to the synthesis media toaid in and/or guide the polymerization and/or polycondensing and/ororganization of the building blocks that form the organosilica materialframework. Further, a “porogen” is understood to be a compound capableof forming voids or pores in the resultant organosilica materialframework. As used herein, the term “structure directing agent”encompasses and is synonymous and interchangeable with the terms“templating agent” and “template.”

As used herein, and unless otherwise specified, the term “adsorption”includes physisorption, chemisorption, and condensation onto a solidmaterial and combinations thereof.

II. ADSORBENT MATERIAL

The invention relates to an adsorbent material, particularly forseparation of heteroatom species. In a first embodiment, an adsorbentmaterial is provided comprising: (i) a porous material support; and (ii)about 0.5 wt. % to about 30 wt. % of a Group metal ion.

In various aspects, the porous material support may be selected from thegroup consisting of an organosilica material support, which is a polymercomprising independent units of a monomer of Formula [Z¹OZ²OSiCH₂]₃ (I),wherein Z¹ and Z² each independently can be a hydrogen atom, a C₁-C₄alkyl group or a bond to a silicon atom of another monomer; anothersiliceous material; and a combination thereof, and (ii) at least onecatalyst metal selected from the group consisting of a Group 8 metal, aGroup 9 metal, a Group 10 metal and a combination thereof.

As used herein, and unless otherwise specified, “a bond to a siliconatom of another monomer” means the bond can advantageously displace amoiety (particularly an oxygen-containing moiety such as a hydroxyl, analkoxy or the like), if present, on a silicon atom of the anothermonomer so there may be a bond directly to the silicon atom of theanother monomer thereby connecting the two monomers, e.g., via a Si—O—Silinkage. For clarity, in this bonding scenario, the “another monomer”can be a monomer of the same type or a monomer of a different type.

II.A. Porous Material Support—Organosilica Material

1. Monomers of Formula (I)

In various embodiments, the porous material support may be anorganosilica material. In particular, the organosilica material can be apolymer comprising independent units of a monomer of Formula[Z¹OZ²OSiCH₂]₃ (I), wherein Z¹ and/or Z² each can be a hydrogen atom.

Additionally or alternatively, Z¹ and/or Z² each can be a C₁-C₄ alkylgroup, a C₁-C₃ alkyl group, a C₁-C₂ alkyl group or methyl.

Additionally or alternatively, Z¹ and/or Z² each can be a bond to asilicon atom of another siloxane monomer.

Additionally or alternatively, Z¹ and Z² each independently can be ahydrogen atom, a C₁-C₂ alkyl group or a bond to a silicon atom ofanother monomer.

In a particular embodiment, Z¹ and Z² each independently can be ahydrogen atom, ethyl or a bond to a silicon atom of another monomer.

In another particular embodiment, Z¹ and Z² each independently can be ahydrogen atom or a bond to a silicon atom of another monomer.

2. Monomers of Formula (II)

In various embodiments, the organosilica material may further compriseanother monomer in combination with independent units of Formula (I),such as another monomer having at least one independent unit of Formula[Z³OZ⁴SiCH₂]₃ (II), wherein each Z³ represents a hydrogen atom, a C₁-C₄alkyl group or a bond to a silicon atom of another monomer and Z⁴represents a C₁-C₆ alkyl group;

In various embodiments, each Z³ can be a hydrogen atom.

Additionally or alternatively, each Z³ can be a C₁-C₄ alkyl group, aC₁-C₃ alkyl group, a C₁-C₂ alkyl group or methyl.

Additionally or alternatively, each Z³ can be a hydrogen atom or a C₁-C₂alkyl group.

Additionally or alternatively, each Z³ can be a bond to a silicon atomof another monomer.

Additionally or alternatively, each Z³ can be a hydrogen atom, a C₁-C₂alkyl group or a bond to a silicon atom of another monomer.

Additionally or alternatively, each Z³ can be a hydrogen atom, ethyl ora bond to a silicon atom of another monomer.

Additionally or alternatively, each Z⁴ can be a C₁-C₆ alkyl group, aC₁-C₅ alkyl group, a C₁-C₄ alkyl group, a C₁-C₃ alkyl group, a C₁-C₂alkyl group or methyl. In particular, Z⁴ can be methyl.

Additionally or alternatively, each Z³ can be a hydrogen atom, a C₁-C₂alkyl group or a bond to a silicon atom of another monomer and each Z⁴can be a C₁-C₄ alkyl group.

Additionally or alternatively, each Z³ can be a hydrogen atom, ethyl ora bond to a silicon atom of another monomer and each Z⁴ can be methyl.

Additionally or alternatively, each Z³ can be a hydrogen atom or a bondto a silicon atom of another monomer and each Z⁴ can be methyl.

3. Monomers of Formula (III)

In various embodiments, the organosilica material may further compriseanother monomer in combination with independent units of Formula (I) andoptionally independent units of Formula (II), such as another monomerhaving at least one independent unit of Formula Z⁵OZ⁶Z⁷Z⁸Si (III),wherein each Z⁵ can be a hydrogen atom, a C₁-C₄ alkyl group or a bond toa silicon atom of another monomer; and Z⁶, Z⁷ and Z⁸ each independentlycan be selected from the group consisting of a hydroxyl group, a C₁-C₄alkyl group, a C₁-C₄ alkoxy group, a nitrogen-containing C₁-C₁₀ alkylgroup, a nitrogen-containing heteroaralkyl group, and anitrogen-containing optionally substituted heterocycloalkyl group, andan oxygen atom bonded to a silicon atom of another monomer.

As used herein, and unless otherwise specified, “an oxygen atom bondedto a silicon atom of another monomer” means that the oxygen atom canadvantageously displace a moiety (particularly an oxygen-containingmoiety such as a hydroxyl, an alkoxy or the like), if present, on asilicon atom of the another monomer so the oxygen atom may be bondeddirectly to the silicon atom of the another monomer thereby connectingthe two monomers, e.g., via a Si—O—Si linkage. For clarity, in thisbonding scenario, the “another monomer” can be a monomer of the sametype or a monomer of a different type.

Additionally or alternatively, each Z⁵ can be a hydrogen atom, a C₁-C₄alkyl group or a bond to a silicon atom of another monomer; and Z⁶, Z⁷and Z⁸ each independently can be selected from the group consisting of ahydroxyl group, a C₁-C₄ alkyl group, a C₁-C₄ alkoxy group, and an oxygenatom bonded to a silicon atom of another monomer. Additionally oralternatively, Z⁶, Z⁷ and Z⁸ each independently can optionally be anitrogen-containing C₁-C₁₀ alkyl group, a nitrogen-containingheteroaralkyl group, and/or a nitrogen-containing optionally substitutedheterocycloalkyl group.

In various aspects, each Z⁵ can be a hydrogen atom.

Additionally or alternatively, each Z⁵ can be a C₁-C₄ alkyl group, aC₁-C₃ alkyl group, a C₁-C₂ alkyl group or methyl.

Additionally or alternatively, each Z⁵ can be a hydrogen atom or a C₁-C₂alkyl group.

Additionally or alternatively, each Z⁵ can be a bond to a silicon atomof another monomer.

Additionally or alternatively, each Z⁵ can be a hydrogen atom, a C₁-C₂alkyl group or a bond to a silicon atom of another monomer.

Additionally or alternatively, each Z⁵ can be a hydrogen atom, ethyl,methyl or a bond to a silicon atom of another monomer.

Additionally or alternatively, Z⁶, Z⁷ and Z⁸ each independently can be ahydroxyl group.

Additionally or alternatively, each Z⁵ can be a hydrogen atom, a C₁-C₂alkyl group or a bond to a silicon atom of another monomer; and Z⁶, Z⁷and Z⁸ each independently can be a hydroxyl group.

Additionally or alternatively, Z⁶, Z⁷ and Z⁸ each independently can be aC₁-C₄ alkyl group, a C₁-C₃ alkyl group, a C₁-C₂ alkyl group or methyl.

Additionally or alternatively, Z⁶, Z⁷ and Z⁸ each independently can be ahydroxyl group or a C₁-C₂ alkyl group.

Additionally or alternatively, each Z⁵ can be a hydrogen atom, a C₁-C₂alkyl group or a bond to a silicon atom of another monomer; and Z⁶, Z⁷and Z⁸ each independently can be a hydroxyl group or a C₁-C₂ alkylgroup.

Additionally or alternatively, Z⁶, Z⁷ and Z⁸ each independently can be aC₁-C₄ alkoxy group, a C₁-C₃ alkoxy group, a C₁-C₂ alkoxy group ormethoxy.

Additionally or alternatively, Z⁶, Z⁷ and Z⁸ each independently can beselected from the group consisting of a hydroxyl group, a C₁-C₂ alkylgroup and a C₁-C₂ alkoxy group.

Additionally or alternatively, each Z⁵ can be a hydrogen atom, a C₁-C₂alkyl group or a bond to a silicon atom of another monomer; and Z⁶, Z⁷and Z⁸ each can be selected from the group consisting of a hydroxylgroup, a C₁-C₂ alkyl group and a C₁-C₂ alkoxy group.

Additionally or alternatively, Z⁶, Z⁷ and Z⁸ each independently canoptionally be a nitrogen-containing C₁-C₁₀ alkyl group, anitrogen-containing C₁-C₉ alkyl group, a nitrogen-containing C₁-C₈ alkylgroup, a nitrogen-containing C₁-C₇ alkyl group, a nitrogen-containingC₁-C₆ alkyl group, a nitrogen-containing C₁-C₅ alkyl group, anitrogen-containing C₁-C₄ alkyl group, a nitrogen-containing C₁-C₃ alkylgroup, a nitrogen-containing C₁-C₂ alkyl group, or a methylamine. Inparticular, Z⁶, Z⁷ and Z⁸ each independently can be anitrogen-containing C₂-C₁₀ alkyl group, a nitrogen-containing C₃-C₁₀alkyl group, a nitrogen-containing C₃-C₉ alkyl group, or anitrogen-containing C₃-C₈ alkyl group. The aforementionednitrogen-containing alkyl groups may have one or more nitrogen atoms(e.g., 2, 3, etc.). Examples of nitrogen-containing C₁-C₁₀ alkyl groupsinclude, but are not limited to,

Additionally or alternatively, Z⁶, Z⁷ and Z⁸ each independently can beselected from the group consisting of a hydroxyl group, a C₁-C₂ alkylgroup, a C₁-C₂ alkoxy group and a nitrogen-containing C₃-C₁₀ alkylgroup.

Additionally or alternatively, each Z⁵ can be a hydrogen atom, a C₁-C₂alkyl group or a bond to a silicon atom of another monomer; and Z⁶, Z⁷and Z⁸ each independently can be selected from the group consisting of ahydroxyl group, a C₁-C₂ alkyl group, a C₁-C₂ alkoxy group and anitrogen-containing C₃-C₁₀ alkyl group.

Additionally or alternatively, Z⁶, Z⁷ and Z⁸ each independently canoptionally be a nitrogen-containing heteroaralkyl group. Thenitrogen-containing heteroaralkyl group can be a nitrogen-containingC₄-C₁₂ heteroaralkyl group, a nitrogen-containing C₄-C₁₀ heteroaralkylgroup, or a nitrogen-containing C₄-C₈ heteroaralkyl group. Examples ofnitrogen-containing heteroaralkyl groups include but are not limited topyridinylethyl, pyridinylpropyl, pyridinylmethyl, indolylmethyl,pyrazinylethyl, and pyrazinylpropyl. The aforementionednitrogen-containing heteroaralkyl groups may have one or more nitrogenatoms (e.g., 2, 3, etc.).

Additionally or alternatively, Z⁶, Z⁷ and Z⁸ each independently can beselected from the group consisting of a hydroxyl group, a C₁-C₂ alkylgroup, a C₁-C₂ alkoxy group, nitrogen-containing C₃-C₁₀ alkyl group anda nitrogen-containing heteroaralkyl group.

Additionally or alternatively, each Z⁵ can be a hydrogen atom, a C₁-C₂alkyl group or a bond to a silicon atom of another monomer; and Z⁶, Z⁷and Z⁸ each independently can be selected from the group consisting of ahydroxyl group, a C₁-C₂ alkyl group, a C₁-C₂ alkoxy group, anitrogen-containing C₃-C₁₀ alkyl group and a nitrogen-containingheteroaralkyl group.

Additionally or alternatively, Z⁶, Z⁷ and Z⁸ each independently canoptionally be a nitrogen-containing heterocycloalkyl group, wherein theheterocycloalkyl group may be optionally substituted with a C₁-C₆ alkylgroup, particularly a C₁-C₄ alkyl group. The nitrogen-containingheterocycloalkyl group can be a nitrogen-containing C₄-C₁₂heterocycloalkyl group, a nitrogen-containing C₄-C₁₀ heterocycloalkylgroup, or a nitrogen-containing C₄-C₈ heterocycloalkyl group. Examplesof nitrogen-containing heterocycloalkyl groups include but are notlimited to piperazinylethyl, piperazinylpropyl, piperidinylethyl,piperidinylpropyl. The aforementioned nitrogen-containingheterocycloalkyl groups may have one or more nitrogen atoms (e.g., 2, 3,etc.).

Additionally or alternatively, Z⁶, Z⁷ and Z⁸ each independently can beselected from the group consisting of a hydroxyl group, a C₁-C₂ alkylgroup, a C₁-C₂ alkoxy group, nitrogen-containing C₃-C₁₀ alkyl group, anitrogen-containing heteroaralkyl group, and a nitrogen-containingoptionally substituted heterocycloalkyl group.

Additionally or alternatively, each Z⁵ can be a hydrogen atom, a C₁-C₂alkyl group or a bond to a silicon atom of another monomer; and Z⁶, Z⁷and Z⁸ each independently can be selected from the group consisting of ahydroxyl group, a C₁-C₂ alkyl group, a C₁-C₂ alkoxy group, anitrogen-containing C₃-C₁₀ alkyl group, a nitrogen-containingheteroaralkyl group and a nitrogen-containing optionally substitutedheterocycloalkyl group.

Additionally or alternatively, Z⁶, Z⁷ and Z⁸ each independently can bean oxygen atom bonded to a silicon atom of another monomer.

Additionally or alternatively, each Z⁵ can be a hydrogen atom, a C₁-C₂alkyl group or a bond to a silicon atom of another monomer; and Z⁶, Z⁷and Z⁸ each independently can be selected from the group consisting of ahydroxyl group, a C₁-C₂ alkyl group, a C₁-C₂ alkoxy group, anitrogen-containing C₃-C₁₀ alkyl group, a nitrogen-containingheteroaralkyl group, a nitrogen-containing optionally substitutedheterocycloalkyl group and an oxygen atom bonded to a silicon atom ofanother monomer.

Additionally or alternatively, each Z⁵ can be a hydrogen atom, a C₁-C₂alkyl group or a bond to a silicon atom of another monomer; and Z⁶, Z⁷and Z⁸ each independently can be selected from the group consisting of ahydroxyl group, a C₁-C₂ alkyl group, a C₁-C₂ alkoxy group, anitrogen-containing C₃-C₈ alkyl group, C₄-C₁₀ heteroaralkyl group, anitrogen-containing optionally substituted C₄-C₁₀ heterocycloalkylgroup, and an oxygen atom bonded to a silicon atom of another monomer.

Additionally or alternatively, each Z⁵ can be a hydrogen atom or a bondto a silicon atom of another monomer; and Z⁶, Z⁷ and Z⁸ eachindependently can be selected from the group consisting of a hydroxylgroup, a C₁-C₂ alkyl group, a nitrogen-containing C₃-C₈ alkyl group,C₄-C₁₀ heteroaralkyl group, a nitrogen-containing optionally substitutedC₄-C₁₀ heterocycloalkyl group, and an oxygen atom bonded to a siliconatom of another monomer.

In a particular embodiment, each Z⁵ can be a hydrogen atom, ethyl or abond to a silicon atom of another monomer; and Z⁶, Z⁷ and Z⁸ eachindependently can be selected from the group consisting of a hydroxylgroup, ethoxy, and an oxygen atom bonded to a silicon atom of anothermonomer.

In another particular embodiment, each Z⁵ can be a hydrogen atom, ethylor a bond to a silicon atom of another comonomer; Z⁶ and Z⁷ eachindependently can be selected from the group consisting of a hydroxylgroup, ethoxy, and an oxygen atom bonded to a silicon atom of anothermonomer; and Z⁸ can be methyl.

In another particular embodiment, each Z⁵ can be a hydrogen atom, methylor a bond to a silicon atom of another comonomer; Z⁶ and Z⁷ eachindependently can be selected from the group consisting of a hydroxylgroup, methoxy, and an oxygen atom bonded to a silicon atom of anothermonomer; and each Z⁸ can be

In another particular embodiment, each Z⁵ can be a hydrogen atom, ethylor a bond to a silicon atom of another comonomer; Z⁶ and Z⁷ eachindependently can be selected from the group consisting of a hydroxylgroup, ethoxy, and an oxygen atom bonded to a silicon atom of anothermonomer; and each Z⁸ can be

In another particular embodiment, each Z⁵ can be a hydrogen atom, ethylor a bond to a silicon atom of another comonomer; Z⁶ and Z⁷ eachindependently can be selected from the group consisting of a hydroxylgroup, ethoxy, and an oxygen atom bonded to a silicon atom of anothermonomer; and each Z⁸ can be

In another particular embodiment, each Z⁵ can be a hydrogen atom, ethylor a bond to a silicon atom of another comonomer; Z⁶ and Z⁷ eachindependently can be selected from the group consisting of a hydroxylgroup, ethoxy, and an oxygen atom bonded to a silicon atom of anothermonomer; and each Z⁸ can be

In another particular embodiment, each Z⁵ can be a hydrogen atom, ethylor a bond to a silicon atom of another comonomer; Z⁶ and Z⁷ eachindependently can be selected from the group consisting of a hydroxylgroup, ethoxy, and an oxygen atom bonded to a silicon atom of anothermonomer; and each Z⁸ can be

In another particular embodiment, each Z⁵ can be a hydrogen atom, ethylor a bond to a silicon atom of another comonomer; Z⁶ and Z⁷ eachindependently can be selected from the group consisting of a hydroxylgroup, ethoxy, and an oxygen atom bonded to a silicon atom of anothermonomer; and each Z⁸ can be

4. Monomers of Formula (IV)

In various embodiments, the organosilica material may further compriseanother monomer in combination with independent units of Formula (I) andoptionally independent units Formula (II) and/or Formula (III), such asanother monomer having at least one independent unit of FormulaZ⁹Z¹Z¹¹Si—R—SiZ⁹Z¹⁰Z¹¹ (IV), wherein each Z⁹ independently can be ahydroxyl group, a C₁-C₄ alkoxy group or an oxygen atom bonded to asilicon atom of another comonomer; each Z¹⁰ and Z¹¹ independently can bea hydroxyl group, a C₁-C₄ alkoxy group, a C₁-C₄ alkyl group or an oxygenatom bonded to a silicon atom of another monomer; and each R can beselected from the group consisting a C₁-C₈ alkylene group, a C₂-C₈alkenylene group, a C₂-C₈ alkynylene group, a nitrogen-containing C₁-C₁₀alkylene group, an optionally substituted C₆-C₂₀ aralkyl and anoptionally substituted C₄-C₂₀ heterocycloalkyl group.

Additionally or alternatively, each Z⁹ independently can be a hydroxylgroup, a C₁-C₄ alkoxy group or an oxygen atom bonded to a silicon atomof another comonomer; each Z¹⁰ and Z¹¹ independently can a hydroxylgroup, a C₁-C₄ alkoxy group, a C₁-C₄ alkyl group or an oxygen atombonded to a silicon atom of another monomer; and each R can be selectedfrom the group consisting a C₁-C₈ alkylene group, a C₂-C₈ alkenylenegroup, and a C₂-C₈ alkynylene group. Additionally or alternatively, Roptionally can be a nitrogen-containing C₁-C₁₀ alkylene group, anoptionally substituted C₆-C₂₀ aralkyl and/or an optionally substitutedC₄-C₂₀ heterocycloalkyl group.

In various aspects, each Z⁹ can be a hydroxyl group.

Additionally or alternatively, each Z⁹ can be a C₁-C₄ alkoxy group, aC₁-C₃ alkoxy group, a C₁-C₂ alkoxy group or methoxy.

Additionally or alternatively, each Z⁹ can be a hydroxyl group or aC₁-C₂ alkoxy group.

Additionally or alternatively, each Z⁹ can be an oxygen atom bonded to asilicon atom of another comonomer.

Additionally or alternatively, each Z⁹ can be a hydroxyl group, a C₁-C₂alkoxy group or an oxygen atom bonded to a silicon atom of anothercomonomer.

Additionally or alternatively, each Z⁹ can be a hydroxyl group or anoxygen atom bonded to a silicon atom of another comonomer.

Additionally or alternatively, each Z¹⁰ and Z¹¹ independently can be ahydroxyl group.

Additionally or alternatively, each Z¹⁰ and Z¹¹ independently can be aC₁-C₄ alkoxy group, a C₁-C₃ alkoxy group, a C₁-C₂ alkoxy group ormethoxy.

Additionally or alternatively, each Z¹⁰ and Z¹¹ independently can be ahydroxyl group or a C₁-C₂ alkoxy group.

Additionally or alternatively, each Z¹⁰ and Z¹¹ independently can be aC₁-C₄ alkyl group, a C₁-C₃ alkyl group, a C₁-C₂ alkyl group or methyl.

Additionally or alternatively, each Z¹⁰ and Z¹¹ independently can be ahydroxyl group, a C₁-C₂ alkoxy group, or a C₁-C₂ alkyl group.

Additionally or alternatively, each Z¹⁰ and Z¹¹ independently can be anoxygen atom bonded to a silicon atom of another comonomer.

Additionally or alternatively, each Z¹⁰ and Z¹¹ independently can be ahydroxyl group, a C₁-C₂ alkoxy group, a C₁-C₂ alkyl group, or an oxygenatom bonded to a silicon atom of another comonomer.

Additionally or alternatively, each Z¹⁰ and Z¹¹ independently can be ahydroxyl group, a C₁-C₂ alkyl group, or an oxygen atom bonded to asilicon atom of another comonomer.

Additionally or alternatively, each Z⁹ can be a hydroxyl group, a C₁-C₂alkoxy group or an oxygen atom bonded to a silicon atom of anothercomonomer; and each Z¹⁰ and Z¹¹ independently can be a hydroxyl group, aC₁-C₂ alkoxy group, a C₁-C₂ alkyl group, or an oxygen atom bonded to asilicon atom of another comonomer.

Additionally or alternatively, each Z⁹ can be a hydroxyl group, ethoxy,methoxy or an oxygen atom bonded to a silicon atom of another comonomer;and each Z¹⁰ and Z¹¹ independently can be a hydroxyl group, ethoxy,methyl, or an oxygen atom bonded to a silicon atom of another comonomer.

Additionally or alternatively, each Z⁹ can be a hydroxyl group or anoxygen atom bonded to a silicon atom of another comonomer; and each Z¹⁰and Z¹¹ independently can be a hydroxyl group, methyl, or an oxygen atombonded to a silicon atom of another comonomer.

Additionally or alternatively, each R can be a C₁-C₈ alkylene group, aC₁-C₇ alkylene group, a C₁-C₆ alkylene group, a C₁-C₅ alkylene group, aC₁-C₄ alkylene group, a C₁-C₃ alkylene group, a C₁-C₂ alkylene group or—CH₂—.

Additionally or alternatively, each Z⁹ can be a hydroxyl group, a C₁-C₂alkoxy group or an oxygen atom bonded to a silicon atom of anothercomonomer; each Z¹⁰ and Z¹¹ independently can be a hydroxyl group, aC₁-C₂ alkoxy group, a C₁-C₂ alkyl group, or an oxygen atom bonded to asilicon atom of another comonomer; and each R can be a C₁-C₄ alkylenegroup.

Additionally or alternatively, each R can be a C₂-C₈ alkenylene group, aC₂-C₇ alkenylene group, a C₂-C₆ alkenylene group, a C₂-C₅ alkenylenegroup, a C₂-C₄ alkenylene group, a C₂-C₃ alkenylene group, or —HC═CH—.

Additionally or alternatively, each Z⁹ can be a hydroxyl group, a C₁-C₂alkoxy group or an oxygen atom bonded to a silicon atom of anothercomonomer; each Z¹⁰ and Z¹¹ independently can be a hydroxyl group, aC₁-C₂ alkoxy group, a C₁-C₂ alkyl group, or an oxygen atom bonded to asilicon atom of another comonomer; and each R can be selected from thegroup consisting of a C₁-C₄ alkylene group and a C₂-C₄ alkenylene group.

Additionally or alternatively, each R can be a C₂-C₈ alkynylene group, aC₂-C₇ alkynylene group, a C₂-C₆ alkynylene group, a C₂-C₅ alkynylenegroup, a C₂-C₄ alkynylene group, a C₂-C₃ alkynylene group, or —C≡C—.

Additionally or alternatively, each Z⁹ can be a hydroxyl group, a C₁-C₂alkoxy group or an oxygen atom bonded to a silicon atom of anothercomonomer; each Z¹⁰ and Z¹¹ independently can be a hydroxyl group, aC₁-C₂ alkoxy group, a C₁-C₂ alkyl group, or an oxygen atom bonded to asilicon atom of another comonomer; and each R can be selected from thegroup consisting of a C₁-C₄ alkylene group, a C₂-C₄ alkenylene group anda C₂-C₄ alkynylene group.

Additionally or alternatively, each R can be a nitrogen-containingC₂-C₁₀ alkylene group, a nitrogen-containing C₃-C₁₀ alkylene group, anitrogen-containing C₄-C₁₀ alkylene group, a nitrogen-containing C₄-C₉alkylene group, a nitrogen-containing C₄-C₈ alkylene group, or nitrogencontaining C₃-C₈ alkylene group. The aforementioned nitrogen-containingalkylene groups may have one or more nitrogen atoms (e.g., 2, 3, etc.).Examples of nitrogen-containing alkylene groups include, but are notlimited to,

Additionally or alternatively, each Z⁹ can be a hydroxyl group, a C₁-C₂alkoxy group or an oxygen atom bonded to a silicon atom of anothercomonomer; each Z¹⁰ and Z¹¹ independently can be a hydroxyl group, aC₁-C₂ alkoxy group, a C₁-C₂ alkyl group, or an oxygen atom bonded to asilicon atom of another comonomer; and each R can be selected from thegroup consisting of a C₁-C₄ alkylene group, a C₂-C₄ alkenylene group, aC₂-C₄ alkynylene group and a nitrogen-containing C₄-C₁₀ alkylene group.

Additionally or alternatively, each R can be an optionally substitutedC₆-C₂₀ aralkyl, an optionally substituted C₆-C₁₄ aralkyl, or anoptionally substituted C₆-C₁₀ aralkyl. Examples of C₆-C₂₀ aralkylsinclude, but are not limited to, phenylmethyl, phenylethyl, andnaphthylmethyl. The aralkyl may be optionally substituted with a C₁-C₆alkyl group, particularly a C₁-C₄ alkyl group.

Additionally or alternatively, each Z⁹ can be a hydroxyl group, a C₁-C₂alkoxy group or an oxygen atom bonded to a silicon atom of anothercomonomer; each Z¹⁰ and Z¹¹ independently can be a hydroxyl group, aC₁-C₂ alkoxy group, a C₁-C₂ alkyl group, or an oxygen atom bonded to asilicon atom of another comonomer; and R can be selected from the groupconsisting of a C₁-C₄ alkylene group, a C₂-C₄ alkenylene group, a C₂-C₄alkynylene group, a nitrogen-containing C₄-C₁₀ alkylene group and anoptionally substituted C₆-C₁₀ aralkyl.

Additionally or alternatively, each R can be an optionally substitutedC₄-C₂₀ heterocycloalkyl group, an optionally substituted C₄-C₁₆heterocycloalkyl group, an optionally substituted C₄-C₁₂heterocycloalkyl group, or an optionally substituted C₄-C₁₀heterocycloalkyl group. Examples of C₄-C₂₀ heterocycloalkyl groupsinclude, but are not limited to, thienylmethyl, furylethyl,pyrrolylmethyl, piperazinylethyl, pyridylmethyl, benzoxazolylethyl,quinolinylpropyl, and imidazolylpropyl. The heterocycloalkyl may beoptionally substituted with a C₁-C₆ alkyl group, particularly a C₁-C₄alkyl group.

Additionally or alternatively, each Z⁹ can be a hydroxyl group, a C₁-C₂alkoxy group or an oxygen atom bonded to a silicon atom of anothercomonomer; each Z¹⁰ and Z¹¹ independently can be a hydroxyl group, aC₁-C₂ alkoxy group, a C₁-C₂ alkyl group, or an oxygen atom bonded to asilicon atom of another comonomer; and R can be selected from the groupconsisting of a C₁-C₄ alkylene group, a C₂-C₄ alkenylene group, a C₂-C₄alkynylene group, a nitrogen-containing C₄-C₁₀ alkylene group, anoptionally substituted C₆-C₁₀ aralkyl and an optionally substitutedC₄-C₁₀ heterocycloalkyl group.

Additionally or alternatively, each Z⁹ can be a hydroxyl group, ethoxy,methoxy or an oxygen atom bonded to a silicon atom of another comonomer;each Z¹⁰ and Z¹¹ independently can be a hydroxyl group, ethoxy, methoxy,methyl, or an oxygen atom bonded to a silicon atom of another comonomer;and R can be selected from the group consisting of —CH₂—, —CH₂CH₂—,—HC═CH—,

Additionally or alternatively, each Z⁹ can be a hydroxyl group or anoxygen atom bonded to a silicon atom of another comonomer; each Z¹⁰ andZ¹¹ independently can be a hydroxyl group, methyl, or an oxygen atombonded to a silicon atom of another comonomer; and each R can beselected from the group consisting of —CH₂—, —CH₂CH₂—, —HC═CH—,

In a particular embodiment, each Z⁹ can be a hydroxyl group, ethoxy oran oxygen atom bonded to a silicon atom of another comonomer; each Z¹⁰can be a hydroxyl group, ethoxy, and an oxygen atom bonded to a siliconatom of another monomer; each Z¹¹ can be methyl; and each R can be—CH₂CH₂—.

In another particular embodiment, each Z⁹ can be a hydroxyl group,ethoxy or an oxygen atom bonded to a silicon atom of another comonomer;each Z¹⁰ and Z¹¹ independently can be selected from the group consistingof a hydroxyl group, ethoxy, and an oxygen atom bonded to a silicon atomof another monomer; and R can be

—CH₂—.

In another particular embodiment, each Z⁹ can be a hydroxyl group,ethoxy or an oxygen atom bonded to a silicon atom of another comonomer;each Z¹⁰ and Z¹¹ independently can be selected from the group consistingof a hydroxyl group, ethoxy, and an oxygen atom bonded to a silicon atomof another monomer; and R can be

—HC═CH—.

In another particular embodiment, each Z⁹ can be a hydroxyl group,methoxy or an oxygen atom bonded to a silicon atom of another comonomer;each Z¹⁰ and Z¹¹ independently can be selected from the group consistingof a hydroxyl group, methoxy, and an oxygen atom bonded to a siliconatom of another monomer; and each R can be

In another particular embodiment, each Z⁹ can be a hydroxyl group,ethoxy or an oxygen atom bonded to a silicon atom of another comonomer;Z¹⁰ can be a hydroxyl group, ethoxy, and an oxygen atom bonded to asilicon atom of another monomer; Z¹¹ can be methyl; and each R can be

In another particular embodiment, each Z⁹ can be a hydroxyl group,methoxy or an oxygen atom bonded to a silicon atom of another comonomer;Z¹⁰ can be a hydroxyl group, methoxy, and an oxygen atom bonded to asilicon atom of another monomer; Z¹¹ can be methyl; and each R can be

5. Monomers of Formula (V)

In various embodiments, the organosilica material may further compriseanother monomer in combination with independent units of Formula (I) andoptionally independent units Formula (II), (III), and/or (IV), such asanother monomer having at least one independent cyclic polyurea monomerof Formula

wherein each R¹ independently is a X¹OX²X³SiX⁴ group, wherein each X¹represents a hydrogen atom, a C₁-C₄ alkyl group or a bond to a siliconatom of another monomer unit; X² and X³ each independently represent ahydroxyl group, a C₁-C₄ alkyl group, a C₁-C₄ alkoxy group or an oxygenatom bonded to a silicon atom of another monomer unit; and each X⁴represents a C₁-C₈ alkylene group bonded to a nitrogen atom of thecyclic polyurea.

In various embodiments, each X¹ can be a hydrogen atom.

Additionally or alternatively, each X¹ can be a C₁-C₄ alkyl group, aC₁-C₃ alkyl group, a C₁-C₂ alkyl group or methyl.

Additionally or alternatively, each X¹ can be a bond to a silicon atomof another siloxane monomer.

Additionally or alternatively, each X¹ can be a hydrogen atom, a C₁-C₂alkyl group or a bond to a silicon atom of another monomer.

Additionally or alternatively, X² and X³ each independently can be ahydroxyl group.

Additionally or alternatively, X² and X³ each independently can be aC₁-C₄ alkyl group, a C₁-C₃ alkyl group, a C₁-C₂ alkyl group or methyl.

Additionally or alternatively, X² and X³ each independently can be aC₁-C₄ alkoxy group, a C₁-C₃ alkoxy group, a C₁-C₂ alkoxy group ormethoxy.

Additionally or alternatively, X² and X³ each independently can be anoxygen atom bonded to a silicon atom of another monomer unit.

Additionally or alternatively, X² and X³ each independently can be ahydroxyl group, a C₁-C₂ alkyl group, a C₁-C₂ alkoxy group, or an oxygenatom bonded to a silicon atom of another monomer unit.

Additionally or alternatively, each X¹ can be a hydrogen atom, a C₁-C₂alkyl group or a bond to a silicon atom of another monomer; and X² andX³ each independently can be a hydroxyl group, a C₁-C₂ alkyl group, aC₁-C₂ alkoxy group, or an oxygen atom bonded to a silicon atom ofanother monomer unit.

Additionally or alternatively, each X⁴ can be a C₁-C₇ alkylene groupbonded to a nitrogen atom of the cyclic polyurea, a C₁-C₇ alkylene groupbonded to a nitrogen atom of the cyclic polyurea, a C₁-C₆ alkylene groupbonded to a nitrogen atom of the cyclic polyurea, a C₁-C₄ alkylene groupbonded to a nitrogen atom of the cyclic polyurea, a C₁-C₃ alkylene groupbonded to a nitrogen atom of the cyclic polyurea, a C₁-C₂ alkylene groupbonded to a nitrogen atom of the cyclic polyurea, or —CH₂— bonded to anitrogen atom of the cyclic polyurea.

Additionally or alternatively, each X¹ can be a hydrogen atom, a C₁-C₂alkyl group or a bond to a silicon atom of another monomer; X² and X³each independently can be a hydroxyl group, a C₁-C₂ alkyl group, a C₁-C₂alkoxy group, or an oxygen atom bonded to a silicon atom of anothermonomer unit; and X⁴ can be a C₁-C₄ alkylene group bonded to a nitrogenatom of the cyclic polyurea.

Additionally or alternatively, each X¹ can be a hydrogen atom or a bondto a silicon atom of another monomer; X² and X³ each independently canbe a hydroxyl group, a C₁-C₂ alkyl group or an oxygen atom bonded to asilicon atom of another monomer unit; and X⁴ can be a C₁-C₄ alkylenegroup bonded to a nitrogen atom of the cyclic polyurea.

Additionally or alternatively, each X¹ can be a hydrogen atom or a bondto a silicon atom of another monomer; X² and X³ each independently canbe a hydroxyl group or an oxygen atom bonded to a silicon atom ofanother monomer unit; and X⁴ can be a C₁-C₄ alkylene group bonded to anitrogen atom of the cyclic polyurea.

In a particular embodiment, each X¹ can be a hydrogen atom, methyl, or abond to a silicon atom of another monomer; X² and X³ each independentlycan be a hydroxyl group, methoxy or an oxygen atom bonded to a siliconatom of another monomer unit; and X⁴ can be —CH₂CH₂CH₂— bonded to anitrogen atom of the cyclic polyurea.

6. Monomers of Formula (VI)

In various embodiments, the organosilica material may further compriseanother monomer in combination with independent units of Formula (I) andoptionally independent units Formula (II), (III), (IV) and/or (V), suchas another monomer having at least one independent unit of FormulaM¹(OZ¹²)₃ (VI), wherein M¹ represents a Group 13 metal and each Z¹²independently represents a hydrogen atom, a C₁-C₆ alkyl or a bond to asilicon atom of another monomer;

Additionally or alternatively, M¹ can be B, Al, Ga, IN Tl, or Uut. Inparticular, M¹ can be Al or B.

Additionally or alternatively, each Z¹² can be a hydrogen atom.

Additionally or alternatively, M¹ can be Al or B and Z¹² can be ahydrogen atom.

Additionally or alternatively, each Z¹² can be a C₁-C₆ alkyl group, aC₁-C₅ alkyl group, a C₁-C₄ alkyl group, a C₁-C₃ alkyl group, a C₁-C₂alkyl group or methyl. In particular, X¹ can be methyl, ethyl, propyl orbutyl.

Additionally or alternatively, M¹ can be Al or B and each Z¹² can be ahydrogen atom, methyl, ethyl, propyl or butyl.

Additionally or alternatively, each Z¹² can be a bond to a silicon atomof another monomer.

Additionally or alternatively, M¹ can be Al or B and each Z¹² can be ahydrogen atom, methyl, ethyl, propyl, butyl or a bond to a silicon atomof another monomer.

Additionally or alternatively, M¹ can be Al or B and each Z¹² can be ahydrogen atom or a bond to a silicon atom of another monomer.

Additionally or alternatively, M¹ can be Al and each Z¹² can be ahydrogen atom, methyl, ethyl, propyl, butyl or a bond to a silicon atomof another monomer.

In a particular embodiment, M¹ can be Al and each Z¹² can be a hydrogenatom, methyl or a bond to a silicon atom of another monomer.

In another particular embodiment, M¹ can be Al and each Z¹² can be ahydrogen atom, ethyl or a bond to a silicon atom of another monomer.

In another particular embodiment, M¹ can be Al and each Z¹² can be ahydrogen atom, propyl or a bond to a silicon atom of another monomer.

In another particular embodiment, M¹ can be Al and each Z¹² can be ahydrogen atom, butyl or a bond to a silicon atom of another monomer.

In another particular embodiment, M¹ can be Al or B; and each Z^(u) canbe a hydrogen atom or a bond to a silicon atom of another monomer.

7. Monomers of Formula (VII)

In various embodiments, the organosilica material may further compriseanother monomer in combination with independent units of Formula (I) andoptionally independent units Formula (II), (III) and/or Formula (IV),such as another monomer having at least one independent unit of Formula(Z¹³O)₂M²-O—Si(OZ¹⁴)₃ (VII), wherein M² represents a Group 13 metal andZ¹³ and Z¹⁴ each independently represent a hydrogen atom, a C₁-C₆ alkylgroup or a bond to a silicon atom of another monomer.

Additionally or alternatively, M² can be B, Al, Ga, IN Tl, or Uut. Inparticular, M² can be Al or B.

Additionally or alternatively, Z¹³ and/or Z¹⁴ each can be a hydrogenatom.

Additionally or alternatively, M² can be Al or B and Z¹¹ and/or Z¹⁴ eachcan be a hydrogen atom.

Additionally or alternatively, Z¹³ and/or Z¹⁴ each can be a C₁-C₆ alkylgroup, a C₁-C₅ alkyl group, a C₁-C₄ alkyl group, a C₁-C₃ alkyl group, aC₁-C₂ alkyl group or methyl. In particular, Z¹³ and/or Z¹⁴ can bemethyl, ethyl, propyl or butyl.

Additionally or alternatively, M² can be Al or B; and Z¹³ and/or Z¹⁴each independently can be a hydrogen atom, methyl, ethyl, propyl orbutyl.

Additionally or alternatively, Z¹³ and/or Z¹⁴ each can be a bond to asilicon atom of another monomer.

Additionally or alternatively, M² can be Al or B; and Z¹³ and Z¹⁴ eachindependently can be a hydrogen atom, methyl, ethyl, propyl, butyl or abond to a silicon atom of another monomer.

Additionally or alternatively, M² can be Al or B; and Z¹³ and Z¹⁴ eachindependently can be a hydrogen atom or a bond to a silicon atom ofanother monomer.

Additionally or alternatively, M² can be Al; and Z¹³ and Z¹⁴ eachindependently can be a hydrogen atom, methyl, ethyl, propyl, butyl or abond to a silicon atom of another monomer.

In a particular embodiment, M² can be Al; and Z¹³ and Z¹⁴ eachindependently can be a hydrogen atom, methyl or a bond to a silicon atomof another monomer.

In another particular embodiment, M² can be Al; and Z¹³ and Z¹⁴ eachindependently can be a hydrogen atom, ethyl or a bond to a silicon atomof another monomer.

In another particular embodiment, M² can be Al; and Z¹³ and Z¹⁴ eachindependently can be a hydrogen atom, propyl or a bond to a silicon atomof another monomer.

In another particular embodiment, M² can be Al; and Z¹³ and Z¹⁴ eachindependently can be a hydrogen atom, butyl or a bond to a silicon atomof another monomer.

In another particular embodiment, M² can be Al or B; and Z¹³ and Z¹⁴each independently can be a hydrogen atom or a bond to a silicon atom ofanother monomer.

The organosilica material described herein can be characterized asdescribed in the following sections.

8. X-Ray Diffraction Peaks

The organosilica materials described herein can exhibit powder X-raydiffraction patterns with one peak between about 1 and about 4 degrees2θ, particularly one peak between about 1 and about 3 degrees 2θ orbetween about 1 and about 2 degrees 2θ. Additionally or alternatively,the organosilica materials can exhibit substantially no peaks in therange of about 0.5 to about 10 degrees 2θ, about 0.5 to about 12 degrees2θ range, about 0.5 to about 15 degrees 2θ, about 0.5 to about 20degrees 2θ, about 0.5 to about 30 degrees 2θ, about 0.5 to about 40degrees 2θ, about 0.5 to about 50 degrees 2θ, about 0.5 to about 60degrees 2θ, about 0.5 to about 70 degrees 2θ, about 2 to about 10degrees 2θ, about 2 to about 12 degrees 2θ range, about 2 to about 15degrees 2θ, about 2 to about 20 degrees 2θ, about 2 to about 30 degrees2θ, about 2 to about 40 degrees 2θ, about 2 to about 50 degrees 2θ,about 2 to about 60 degrees 2θ, about 2 to about 70 degrees 2θ, about 3to about 10 degrees 2θ, about 3 to about 12 degrees 2θ range, about 3 toabout 15 degrees 2θ, about 3 to about 20 degrees 2θ, about 3 to about 30degrees 2θ, about 3 to about 40 degrees 2θ, about 3 to about 50 degrees2θ, about 3 to about 60 degrees 2θ, or about 3 to about 70 degrees 2θ.

9. Silanol Content

The organosilica materials described can have a silanol content thatvaries within wide limits, depending on the composition of the synthesissolution. The silanol content can conveniently be determined by solidstate silicon NMR.

In various aspects, the organosilica materials can have a silanolcontent of greater than about 5%, greater than about 10%, greater thanabout 15%, greater than about 20%, greater than about 25%, greater thanabout 30%, greater than about 33%, greater than 35%, greater than about40%, greater than about 41%, greater than about 44%, greater than about45%, greater than about 50%, greater than about 55%, greater than about60%, greater than about 65%, greater than about 70%, greater than about75%, or about 80%. In certain embodiments, the silanol content can begreater than about 30% or greater than about 41%.

Additionally or alternatively, the organosilica materials may have asilanol content of about 5% to about 80%, about 5% to about 75%, about5% to about 70%, about 5% to about 65%, about 5% to about 60%, about 5%to about 55%, about 5% to about 50%, about 5% to about 45%, about 5% toabout 44%, about 5% to about 41%, about 5% to about 40%, about 5% toabout 35%, about 5% to about 33%, about 5% to about 30%, about 5% toabout 25%, about 5% to about 20%, about 5% to about 15%, about 5% toabout 10%, about 10% to about 80%, about 10% to about 75%, about 10% toabout 70%, about 10% to about 65%, about 10% to about 60%, about 10% toabout 55%, about 10% to about 50%, about 10% to about 45%, about 10% toabout 44%, about 10% to about 41%, about 10% to about 40%, about 10% toabout 35%, about 10% to about 33%, about 10% to about 30%, about 10% toabout 25%, about 10% to about 20%, about 20% to about 80%, about 20% toabout 75%, about 20% to about 70%, about 20% to about 65%, about 20% toabout 60%, about 20% to about 55%, about 20% to about 50%, about 20% toabout 45%, about 20% to about 44%, about 20% to about 41%, about 20% toabout 40%, about 20% to about 35%, about 20% to about 33%, about 20% toabout 30%, about 20% to about 25%, about 30% to about 80%, about 30% toabout 75%, about 30% to about 70%, about 30% to about 65%, about 30% toabout 60%, about 30% to about 55%, about 30% to about 50%, about 30% toabout 45%, about 30% to about 44%, about 30% to about 41%, about 30% toabout 40%, about 30% to about 35%, about 30% to about 33%, about 40% toabout 80%, about 40% to about 75%, about 40% to about 70%, about 40% toabout 65%, about 40% to about 60%, about 40% to about 55%, about 40% toabout 50%, about 40% to about 45%, about 40% to about 44%, or about 40%to about 41%.

10. Pore Size

The organosilica materials described herein are advantageously in amesoporous form. As indicated previously, the term mesoporous refers tosolid materials having pores with a diameter within the range of fromabout 2 nm to about 50 nm. The average pore diameter of the organosilicamaterial can be determined, for example, using nitrogenadsorption-desorption isotherm techniques within the expertise of one ofskill in the art, such as the BET (Brunauer Emmet Teller) method.

The organosilica material supports can have an average pore diameter ofabout 0.2 nm, about 0.4 nm, about 0.5 nm, about 0.6 nm, about 0.8 nm,about 1.0 nm, about 1.5 nm, about 1.8 nm or less than about 2.0 nm.

Additionally or alternatively, the organosilica materials canadvantageously have an average pore diameter within the mesopore rangeof about 2.0 nm, about 2.5 nm, about 3.0 nm, about 3.1 nm, about 3.2 nm,about 3.3 nm, about 3.4 nm, about 3.5 nm, about 3.6 nm, about 3.7 nm,about 3.8 nm, about 3.9 nm about 4.0 nm, about 4.1 nm, about 4.5 nm,about 5.0 nm, about 6.0 nm, about 7.0 nm, about 7.3 nm, about 8 nm,about 8.4 nm, about 9 nm, about 10 nm, about 11 nm, about 13 nm, about15 nm, about 18 nm, about 20 nm, about 23 nm, about 25 nm, about 30 nm,about 40 nm, about 45 nm, or about 50 nm.

Additionally or alternatively, the organosilica materials can have anaverage pore diameter of 0.2 nm to about 50 nm, about 0.2 nm to about 40nm, about 0.2 nm to about 30 nm, about 0.2 nm to about 25 nm, about 0.2nm to about 23 nm, about 0.2 nm to about 20 nm, about 0.2 nm to about 18nm, about 0.2 nm to about 15 nm, about 0.2 nm to about 13 nm, about 0.2nm to about 11 nm, about 0.2 nm to about 10 nm, about 0.2 nm to about 9nm, about 0.2 nm to about 8.4 nm, about 0.2 nm to about 8 nm, about 0.2nm to about 7.3 nm, about 0.2 nm to about 7.0 nm, about 0.2 nm to about6.0 nm, about 0.2 nm to about 5.0 nm, about 0.2 nm to about 4.5 nm,about 0.2 nm to about 4.1 nm, about 0.2 nm to about 4.0 nm, about 0.2 nmto about 3.9 nm, about 0.2 nm to about 3.8 nm, about 0.2 nm to about 3.7nm, about 0.2 nm to about 3.6 nm, about 0.2 nm to about 3.5 nm, about0.2 nm to about 3.4 nm, about 0.2 nm to about 3.3 nm, about 0.2 nm toabout 3.2 nm, about 0.2 nm to about 3.1 nm, about 0.2 nm to about 3.0nm, about 0.2 nm to about 2.5 nm, about 0.2 nm to about 2.0 nm, about0.2 nm to about 1.0 nm, about 1.0 nm to about 50 nm, about 1.0 nm toabout 40 nm, about 1.0 nm to about 30 nm, about 1.0 nm to about 25 nm,about 1.0 nm to about 23 nm, about 1.0 nm to about 20 nm, about 1.0 nmto about 18 nm, about 1.0 nm to about 15 nm, about 1.0 nm to about 13nm, about 1.0 nm to about 11 nm, about 1.0 nm to about 10 nm, about 1.0nm to about 9 nm, about 1.0 nm to about 8.4 nm, about 1.0 nm to about 8nm, about 1.0 nm to about 7.3 nm, about 1.0 nm to about 7.0 nm, about1.0 nm to about 6.0 nm, about 1.0 nm to about 5.0 nm, about 1.0 nm toabout 4.5 nm, about 1.0 nm to about 4.1 nm, about 1.0 nm to about 4.0nm, about 1.0 nm to about 3.9 nm, about 1.0 nm to about 3.8 nm, about1.0 nm to about 3.7 nm, about 1.0 nm to about 3.6 nm, about 1.0 nm toabout 3.5 nm, about 1.0 nm to about 3.4 nm, about 1.0 nm to about 3.3nm, about 1.0 nm to about 3.2 nm, about 1.0 nm to about 3.1 nm, about1.0 nm to about 3.0 nm or about 1.0 nm to about 2.5 nm.

In particular, the organosilica materials can advantageously have anaverage pore diameter in the mesopore range of about 2.0 nm to about 50nm, about 2.0 nm to about 40 nm, about 2.0 nm to about 30 nm, about 2.0nm to about 25 nm, about 2.0 nm to about 23 nm, about 2.0 nm to about 20nm, about 2.0 nm to about 18 nm, about 2.0 nm to about 15 nm, about 2.0nm to about 13 nm, about 2.0 nm to about 11 nm, about 2.0 nm to about 10nm, about 2.0 nm to about 9 nm, about 2.0 nm to about 8.4 nm, about 2.0nm to about 8 nm, about 2.0 nm to about 7.3 nm, about 2.0 nm to about7.0 nm, about 2.0 nm to about 6.0 nm, about 2.0 nm to about 5.0 nm,about 2.0 nm to about 4.5 nm, about 2.0 nm to about 4.1 nm, about 2.0 nmto about 4.0 nm, about 2.0 nm to about 3.9 nm, about 2.0 nm to about 3.8nm, about 2.0 nm to about 3.7 nm, about 2.0 nm to about 3.6 nm, about2.0 nm to about 3.5 nm, about 2.0 nm to about 3.4 nm, about 2.0 nm toabout 3.3 nm, about 2.0 nm to about 3.2 nm, about 2.0 nm to about 3.1nm, about 2.0 nm to about 3.0 nm, about 2.0 nm to about 2.5 nm, about2.5 nm to about 50 nm, about 2.5 nm to about 40 nm, about 2.5 nm toabout 30 nm, about 2.5 nm to about 25 nm, about 2.5 nm to about 23 nm,about 2.5 nm to about 20 nm, about 2.5 nm to about 18 nm, about 2.5 nmto about 15 nm, about 2.5 nm to about 13 nm, about 2.5 nm to about 11nm, about 2.5 nm to about 10 nm, about 2.5 nm to about 9 nm, about 2.5nm to about 8.4 nm, about 2.5 nm to about 8 nm, about 2.5 nm to about7.3 nm, about 2.5 nm to about 7.0 nm, about 2.5 nm to about 6.0 nm,about 2.5 nm to about 5.0 nm, about 2.5 nm to about 4.5 nm, about 2.5 nmto about 4.1 nm, about 2.5 nm to about 4.0 nm, about 2.5 nm to about 3.9nm, about 2.5 nm to about 3.8 nm, about 2.5 nm to about 3.7 nm, about2.5 nm to about 3.6 nm, about 2.5 nm to about 3.5 nm, about 2.5 nm toabout 3.4 nm, about 2.5 nm to about 3.3 nm, about 2.5 nm to about 3.2nm, about 2.5 nm to about 3.1 nm, about 2.5 nm to about 3.0 nm, about3.0 nm to about 50 nm, about 3.0 nm to about 40 nm, about 3.0 nm toabout 30 nm, about 3.0 nm to about 25 nm, about 3.0 nm to about 23 nm,about 3.0 nm to about 20 nm, about 3.0 nm to about 18 nm, about 3.0 nmto about 15 nm, about 3.0 nm to about 13 nm, about 3.0 nm to about 11nm, about 3.0 nm to about 10 nm, about 3.0 nm to about 9 nm, about 3.0nm to about 8.4 nm, about 3.0 nm to about 8 nm, about 3.0 nm to about7.3 nm, about 3.0 nm to about 7.0 nm, about 3.0 nm to about 6.0 nm,about 3.0 nm to about 5.0 nm, about 3.0 nm to about 4.5 nm, about 3.0 nmto about 4.1 nm, or about 3.0 nm to about 4.0 nm.

In one particular embodiment, the organosilicas described herein canhave an average pore diameter of about 1.0 nm to about 30.0 nm,particularly about 1.0 nm to about 25.0 nm, particularly about 2.0 nm toabout 25.0 nm, particularly about 2.0 nm to about 20.0 nm, particularlyabout 2.0 nm to about 15.0 nm, particularly about 2.0 nm to about 10.0nm, or particularly about 3.0 nm to about 10.0 nm.

Using surfactant as a template to synthesize mesoporous materials cancreate highly ordered structure, e.g. well-defined cylindrical-like porechannels. In some circumstances, there may be no hysteresis loopobserved from N₂ adsorption isotherm. In other circumstances, forinstance where mesoporous materials can have less ordered porestructures, a hysteresis loop may be observed from N2 adsorptionisotherm experiments. In such circumstances, without being bound bytheory, the hysteresis can result from the lack of regularity in thepore shapes/sizes and/or from bottleneck constrictions in such irregularpores.

11. Surface Area

The surface area of the organosilica materials can be determined, forexample, using nitrogen adsorption-desorption isotherm techniques withinthe expertise of one of skill in the art, such as the BET (BrunauerEmmet Teller) method. This method may determine a total surface area, anexternal surface area, and a microporous surface area. As used herein,and unless otherwise specified, “total surface area” refers to the totalsurface area as determined by the BET method. As used herein, and unlessotherwise specified, “microporous surface area” refers to microporoussurface are as determined by the BET method.

In various embodiments, the organosilica materials can have a totalsurface area greater than or equal to about 100 m²/g, greater than orequal to about 200 m²/g, greater than or equal to about 300 m²/g,greater than or equal to about 400 m²/g, greater than or equal to about450 m²/g, greater than or equal to about 500 m²/g, greater than or equalto about 550 m²/g, greater than or equal to about 600 m²/g, greater thanor equal to about 700 m²/g, greater than or equal to about 800 m²/g,greater than or equal to about 850 m²/g, greater than or equal to about900 m²/g, greater than or equal to about 1,000 m²/g, greater than orequal to about 1,050 m²/g, greater than or equal to about 1,100 m²/g,greater than or equal to about 1,150 m²/g, greater than or equal toabout 1,200 m²/g, greater than or equal to about 1,250 m²/g, greaterthan or equal to about 1,300 m²/g, greater than or equal to about 1,400m²/g, greater than or equal to about 1,450 m²/g, greater than or equalto about 1,500 m²/g, greater than or equal to about 1,550 m²/g, greaterthan or equal to about 1,600 m²/g, greater than or equal to about 1,700m²/g, greater than or equal to about 1,800 m²/g, greater than or equalto about 1,900 m²/g, greater than or equal to about 2,000 m²/g, greaterthan or equal to greater than or equal to about 2,100 m²/g, greater thanor equal to about 2,200 m²/g, greater than or equal to about 2,300 m²/gor about 2,500 m²/g.

Additionally or alternatively, the organosilicas may have a totalsurface area of about 50 m²/g to about 2,500 m²/g, about 50 m²/g toabout 2,000 m²/g, about 50 m²/g to about 1,500 m²/g, about 50 m²/g toabout 1,000 m²/g, about 100 m²/g to about 2,500 m²/g, about 100 m²/g toabout 2,300 m²/g, about 100 m²/g to about 2,200 m²/g, about 100 m²/g toabout 2,100 m²/g, about 100 m²/g to about 2,000 m²/g, about 100 m²/g toabout 1,900 m²/g, about 100 m²/g to about 1,800 m²/g, about 100 m²/g toabout 1,700 m²/g, about 100 m²/g to about 1,600 m²/g, about 100 m²/g toabout 1,550 m²/g, about 100 m²/g to about 1,500 m²/g, about 100 m²/g toabout 1,450 m²/g, about 100 m²/g to about 1,400 m²/g, about 100 m²/g toabout 1,300 m²/g, about 100 m²/g to about 1,250 m²/g, about 100 m²/g toabout 1,200 m²/g, about 100 m²/g to about 1,150 m²/g, about 100 m²/g toabout 1,100 m²/g, about 100 m²/g to about 1,050 m²/g, about 100 m²/g toabout 1,000 m²/g, about 100 m²/g to about 900 m²/g, about 100 m²/g toabout 850 m²/g, about 100 m²/g to about 800 m²/g, about 100 m²/g toabout 700 m²/g, about 100 m²/g to about 600 m²/g, about 100 m²/g toabout 550 m²/g, about 100 m²/g to about 500 m²/g, about 100 m²/g toabout 450 m²/g, about 100 m²/g to about 400 m²/g, about 100 m²/g toabout 300 m²/g, about 100 m²/g to about 200 m²/g, about 200 m²/g toabout 2,500 m²/g, about 200 m²/g to about 2,300 m²/g, about 200 m²/g toabout 2,200 m²/g, about 200 m²/g to about 2,100 m²/g, about 200 m²/g toabout 2,000 m²/g, about 200 m²/g to about 1,900 m²/g, about 200 m²/g toabout 1,800 m²/g, about 200 m²/g to about 1,700 m²/g, about 200 m²/g toabout 1,600 m²/g, about 200 m²/g to about 1,550 m²/g, about 200 m²/g toabout 1,500 m²/g, about 200 m²/g to about 1,450 m²/g, about 200 m²/g toabout 1,400 m²/g, about 200 m²/g to about 1,300 m²/g, about 200 m²/g toabout 1,250 m²/g, about 200 m²/g to about 1,200 m²/g, about 200 m²/g toabout 1,150 m²/g, about 200 m²/g to about 1,100 m²/g, about 200 m²/g toabout 1,050 m²/g, about 200 m²/g to about 1,000 m²/g, about 200 m²/g toabout 900 m²/g, about 200 m²/g to about 850 m²/g, about 200 m²/g toabout 800 m²/g, about 200 m²/g to about 700 m²/g, about 200 m²/g toabout 600 m²/g, about 200 m²/g to about 550 m²/g, about 200 m²/g toabout 500 m²/g, about 200 m²/g to about 450 m²/g, about 200 m²/g toabout 400 m²/g, about 200 m²/g to about 300 m²/g, about 500 m²/g toabout 2,500 m²/g, about 500 m²/g to about 2,300 m²/g, about 500 m²/g toabout 2,200 m²/g, about 500 m²/g to about 2,100 m²/g, about 500 m²/g toabout 2,000 m²/g, about 500 m²/g to about 1,900 m²/g, about 500 m²/g toabout 1,800 m²/g, about 500 m²/g to about 1,700 m²/g, about 500 m²/g toabout 1,600 m²/g, about 500 m²/g to about 1,550 m²/g, about 500 m²/g toabout 1,500 m²/g, about 500 m²/g to about 1,450 m²/g, about 500 m²/g toabout 1,400 m²/g, about 500 m²/g to about 300 m²/g, about 500 m²/g toabout 1,250 m²/g, about 500 m²/g to about 1,200 m²/g, about 500 m²/g toabout 1,150 m²/g, about 500 m²/g to about 1,100 m²/g, about 500 m²/g toabout 1,050 m²/g, about 500 m²/g to about 1,000 m²/g, about 500 m²/g toabout 900 m²/g, about 500 m²/g to about 850 m²/g, about 500 m²/g toabout 800 m²/g, about 500 m²/g to about 700 m²/g, about 500 m²/g toabout 600 m²/g, about 500 m²/g to about 550 m²/g, about 1,000 m²/g toabout 2,500 m²/g, about 1,000 m²/g to about 2,300 m²/g, about 1,000 m²/gto about 2,200 m²/g, about 1,000 m²/g to about 2,100 m²/g, about 1,000m²/g to about 2,000 m²/g, about 1,000 m²/g to about 1,900 m²/g, about1,000 m²/g to about 1,800 m²/g, about 1,000 m²/g to about 1,700 m²/g,about 1,000 m²/g to about 1,600 m²/g, about 1,000 m²/g to about 1,550m²/g, about 1,000 m²/g to about 1,500 m²/g, about 1,000 m²/g to about1,450 m²/g, about 1,000 m²/g to about 1,400 m²/g, about 1,000 m²/g toabout 1,300 m²/g, about 1,000 m²/g to about 1,250 m²/g, about 1,000 m²/gto about 1,200 m²/g, about 1,000 m²/g to about 1,150 m²/g, about 1,000m²/g to about 1,100 m²/g, or about 1,000 m²/g to about 1,050 m²/g.

In one particular embodiment, the organosilica materials describedherein may have a total surface area of about 200 m²/g to about 2,500m²g, particularly about 400 m²/g to about 2,500 m²g, particularly about400 m²/g to about 2,000 m²/g, particularly about 500 m²/g to about 2,000m²/g, or particularly about 400 m²/g to about 1,500 m²/g.

12. Pore Volume

The pore volume of the organosilica materials described herein can bedetermined, for example, using nitrogen adsorption-desorption isothermtechniques within the expertise of one of skill in the art, such as theBET (Brunauer Emmet Teller) method.

In various embodiments, the organosilica materials can have a porevolume greater than or equal to about 0.1 cm³/g, greater than or equalto about 0.2 cm³/g, greater than or equal to about 0.3 cm³/g, greaterthan or equal to about 0.4 cm³/g, greater than or equal to about 0.5cm³/g, greater than or equal to about 0.6 cm³/g, greater than or equalto about 0.7 cm³/g, greater than or equal to about 0.8 cm³/g, greaterthan or equal to about 0.9 cm³/g, greater than or equal to about 1.0cm³/g, greater than or equal to about 1.1 cm³/g, greater than or equalto about 1.2 cm³/g, greater than or equal to about 1.3 cm³/g, greaterthan or equal to about 1.4 cm³/g, greater than or equal to about 1.5cm³/g, greater than or equal to about 1.6 cm³/g, greater than or equalto about 1.7 cm³/g, greater than or equal to about 1.8 cm³/g, greaterthan or equal to about 1.9 cm³/g, greater than or equal to about 2.0cm³/g, greater than or equal to about 2.5 cm³/g, greater than or equalto about 3.0 cm³/g, greater than or equal to about 3.5 cm³/g, greaterthan or equal to about 4.0 cm³/g, greater than or equal to about 5.0cm³/g, greater than or equal to about 6.0 cm³/g, greater than or equalto about 7.0 cm³/g, or about 10.0 cm³/g.

Additionally or alternatively, the organosilica materials can have apore volume of about 0.1 cm³/g to about 10.0 cm³/g, about 0.1 cm³/g toabout 7.0 cm³/g, about 0.1 cm³/g to about 6.0 cm³/g, about 0.1 cm³/g toabout 5.0 cm³/g, about 0.1 cm³/g to about 4.0 cm³/g, about 0.1 cm³/g toabout 3.5 cm³/g, about 0.1 cm³/g to about 3.0 cm³/g, about 0.1 cm³/g toabout 2.5 cm³/g, about 0.1 cm³/g to about 2.0 cm³/g, about 0.1 cm³/g toabout 1.9 cm³/g, about 0.1 cm³/g to about 1.8 cm³/g, about 0.1 cm³/g toabout 1.7 cm³/g, about 0.1 cm³/g to about 1.6 cm³/g, about 0.1 cm³/g toabout 1.5 cm³/g, about 0.1 cm³/g to about 1.4 cm³/g, about 0.1 cm³/g toabout 1.3 cm³/g, about 0.1 cm³/g to about 1.2 cm³/g, about 0.1 cm³/g toabout 1.1, about 0.1 cm³/g to about 1.0 cm³/g, about 0.1 cm³/g to about0.9 cm³/g, about 0.1 cm³/g to about 0.8 cm³/g, about 0.1 cm³/g to about0.7 cm³/g, about 0.1 cm³/g to about 0.6 cm³/g, about 0.1 cm³/g to about0.5 cm³/g, about 0.1 cm³/g to about 0.4 cm³/g, about 0.1 cm³/g to about0.3 cm³/g, about 0.1 cm³/g to about 0.2 cm³/g, 0.2 cm³/g to about 10.0cm³/g, about 0.2 cm³/g to about 7.0 cm³/g, about 0.2 cm³/g to about 6.0cm³/g, about 0.2 cm³/g to about 5.0 cm³/g, about 0.2 cm³/g to about 4.0cm³/g, about 0.2 cm³/g to about 3.5 cm³/g, about 0.2 cm³/g to about 3.0cm³/g, about 0.2 cm³/g to about 2.5 cm³/g, about 0.2 cm³/g to about 2.0cm³/g, about 0.2 cm³/g to about 1.9 cm³/g, about 0.2 cm³/g to about 1.8cm³/g, about 0.2 cm³/g to about 1.7 cm³/g, about 0.2 cm³/g to about 1.6cm³/g, about 0.2 cm³/g to about 1.5 cm³/g, about 0.2 cm³/g to about 1.4cm³/g, about 0.2 cm³/g to about 1.3 cm³/g, about 0.2 cm³/g to about 1.2cm³/g, about 0.2 cm³/g to about 1.1, about 0.5 cm³/g to about 1.0 cm³/g,about 0.5 cm³/g to about 0.9 cm³/g, about 0.5 cm³/g to about 0.8 cm³/g,about 0.5 cm³/g to about 0.7 cm³/g, about 0.5 cm³/g to about 0.6 cm³/g,about 0.5 cm³/g to about 0.5 cm³/g, about 0.5 cm³/g to about 0.4 cm³/g,about 0.5 cm³/g to about 0.3 cm³/g, 0.5 cm³/g to about 10.0 cm³/g, about0.5 cm³/g to about 7.0 cm³/g, about 0.5 cm³/g to about 6.0 cm³/g, about0.5 cm³/g to about 5.0 cm³/g, about 0.5 cm³/g to about 4.0 cm³/g, about0.5 cm³/g to about 3.5 cm³/g, about 0.5 cm³/g to about 3.0 cm³/g, about0.5 cm³/g to about 2.5 cm³/g, about 0.5 cm³/g to about 2.0 cm³/g, about0.5 cm³/g to about 1.9 cm³/g, about 0.5 cm³/g to about 1.8 cm³/g, about0.5 cm³/g to about 1.7 cm³/g, about 0.5 cm³/g to about 1.6 cm³/g, about0.5 cm³/g to about 1.5 cm³/g, about 0.5 cm³/g to about 1.4 cm³/g, about0.5 cm³/g to about 1.3 cm³/g, about 0.5 cm³/g to about 1.2 cm³/g, about0.5 cm³/g to about 1.1, about 0.5 cm³/g to about 1.0 cm³/g, about 0.5cm³/g to about 0.9 cm³/g, about 0.5 cm³/g to about 0.8 cm³/g, about 0.5cm³/g to about 0.7 cm³/g, or about 0.5 cm³/g to about 0.6 cm³/g.

In a particular embodiment, the organosilica materials can have a porevolume of about 0.1 cm³/g to about 5.0 cm³/g, particularly about 0.1cm³/g to about 3.0 cm³/g, particularly about 0.2 cm³/g to about 3.0cm³/g, particularly about 0.2 cm³/g to about 2.5 cm³/g, or particularlyabout 0.2 cm³/g to about 1.5 cm³/g.

II.B. Porous Material Support—Another Siliceous Material

Additionally or alternatively, the porous material support may beanother siliceous material, alone or in combination with theorganosilica material described herein. Examples of suitable siliceousmaterials include, but are not limited to, silicas (e.g., high surfacearea silicas, ordered mesoporous silicas, amorphous silica, etc.),clays, silica-alumina, phosphate-based crystalline or amorphousmaterials, and combinations thereof. Examples of phosphate-basedcrystalline or amorphous materials include, but are not limited toaluminophosphates (AlPOs), silicoaluminophosphates (SAPOs),metalloaluminophosphates (MeAlPOs; Me=Si, Ti, or Zr) andmetallosilicoaluminophosphates. Examples of ALPO family members include,but are not limited to: ALPO-5, ALPO-11, ALPO-16, ALPO-18, ALPO-22,ALPO-34, ALPO-35, ALPO-47, ALPO-52, ALPO-61, ALPO-AFI, ALPO-kanemite,ALPO4-ZON, ALPO4-L, ALPO4-5, ALPO4-34, and meso-ALPO. Examples of SAPOfamily members include, but are not limited to: SAPO-5, SAPO-8, SAPO-11,SAPO-18, SAPO-23, SAPO-31, SAPO-34, SAPO-35, SAPO-37, SAPO-40, SAPO-44,SAPO-47, SAPO-SOD, SAPO4-L, meso-SAPO. In particular, the siliceousmaterial may be an amorphous silica, such as but not limited to MCM-41,a silica gel, zeolites, and/or amorphous silica alumina.

II.C. Metals

In various embodiments, the adsorbent material can comprise a metaland/or metal ion. The organosilica material can further comprise atleast one metal or metal ion incorporated within the pores of theorganosilica material. Exemplary metals and/or metal ions can include,but are not limited to transition metals and basic metals, such as aGroup 6 element, a Group 7 element, a Group 8 element, a Group 9element, a Group 10 element, a Group 12 element, a Group 13 element or acombination thereof. Exemplary Group 6 elements can include, but are notlimited to, chromium, molybdenum, and/or tungsten, particularlyincluding molybdenum and/or tungsten. Exemplary Group 7 elements caninclude, but are not limited to, manganese, technetium, and/or rhenium,particularly including manganese. Exemplary Group 8 elements caninclude, but are not limited to, iron, ruthenium, and/or osmium.Exemplary Group 9 elements can include, but are not limited to, cobalt,rhodium, and/or iridium, particularly including cobalt. Exemplary Group10 elements can include, but are not limited to, nickel, palladiumand/or platinum. Exemplary Group 12 elements can include, but are notlimited to, zinc, cadmium, and/or mercury, particularly including zinc.Exemplary Group 13 elements can include, but are not limited to, boron,aluminum, and/or gallium, particularly including boron. In a particularembodiment, the adsorbent material can comprise a Group 7 metal or metalion, such as but not limited to, Mn (II) (Mn²⁺) or Mn (III) (Mn³⁺) and acombination thereof. In another particular embodiment, the adsorbentmaterial can comprise a Group 8 metal or metal ion, such as but notlimited to, ferrous iron (iron (II) or Fe²⁺), ferric iron (iron (III) orFe³⁺) and a combination thereof. In another particular embodiment, theadsorbent material can comprise a Group 12 metal or metal ion, such asbut not limited to Zn (II) (Zn²⁺). In another particular embodiment, theadsorbent material can comprise a Group 13 metal or metal ion, such asbut not limited to Al (II) (Al²⁺), Al (III) (Al²⁺) and a combinationthereof.

Additionally or alternatively, the metal or metal ion may be present inan amount of at least about 0.010 wt. %, at least about 0.050 wt. %, atleast about 0.10 wt. %, at least about 0.50 wt. %, at least about 1.0wt. %, at least about 5.0 wt. %, at least about 10 wt. %, at least about15 wt. %, at least about 20 wt. %, at least about 25 wt. %, at leastabout 30 wt. %, at least about 35 wt. %, at least about 40 wt. %, atleast about 45 wt. %, or at least about 50 wt. %. All metals/metal ionweight percents are on finished material. By “finished material” it ismeant that the percents are based on the weight of the finishedadsorbent, i.e., the porous material support with incorporated metal.For example, if the finished adsorbent were to weigh 100 grams, then 20wt. % metal/metal ion would mean that 20 grams of the metal/metal ionwas on 80 gm of the porous support. Additionally or alternatively, themetal or metal ion may be present in an amount of about 0.010 wt. % toabout 50 wt. %, about 0.010 wt. % to about 45 wt. %, about 0.010 wt. %to about 40 wt. %, about 0.010 wt. % to about 35 wt. %, about 0.010 wt.% to about 30 wt. %, about 0.010 wt. % to about 25 wt. %, about 0.010wt. % to about 20 wt. %, about 0.010 wt. % to about 15 wt. %, about0.010 wt. % to about 10 wt. %, about 0.010 wt. % to about 5.0 wt. %,about 0.010 wt. % to about 1.0 wt. %, about 0.010 wt. % to about 0.50wt. %, about 0.010 wt. % to about 0.10 wt. %, about 0.50 wt. % to about50 wt. %, about 0.50 wt. % to about 45 wt. %, about 0.50 wt. % to about40 wt. %, about 0.50 wt. % to about 35 wt. %, about 0.50 wt. % to about30 wt. %, about 0.50 wt. % to about 25 wt. %, about 0.50 wt. % to about20 wt. %, about 0.50 wt. % to about 15 wt. %, about 0.50 wt. % to about10 wt. %, about 0.50 wt. % to about 5.0 wt. %, about 0.50 wt. % to about1.0 wt. %, about 1.0 wt. % to about 50 wt. %, about 1.0 wt. % to about45 wt. %, about 1.0 wt. % to about 40 wt. %, about 1.0 wt. % to about 35wt. %, about 1.0 wt. % to about 30 wt. %, about 1.0 wt. % to about 25wt. %, about 1.0 wt. % to about 20 wt. %, about 1.0 wt. % to about 15wt. %, about 1.0 wt. % to about 10 wt. %, or about 1.0 wt. % to about5.0 wt. %.

In particular, the metal/metal ion may be present in an amount of about0.010 wt. % to about 50 wt. %, about 0.50 wt. % to about 30 wt. %, about0.50 wt. % to about 20 wt. %, about 1.0 wt. % to about 15 wt. % or about1.0 wt. % to about 10 wt. %.

The metal or metal ion can be incorporated into the organosilicamaterial by any convenient method, such as by impregnation, by ionexchange, or by complexation to surface sites.

Additionally or alternatively, the organosilica material can furthercomprise a surface metal incorporated within the pores of theorganosilica material. The surface metal can be selected from a Group 1element, a Group 2 element, a Group 13 element, and a combinationthereof. When a Group 1 element is present, it can preferably compriseor be sodium and/or potassium. When a Group 2 element is present, it caninclude, but may not be limited to, magnesium and/or calcium. When aGroup 13 element is present, it can include, but may not be limited to,boron and/or aluminum.

One or more of the Group 1, 2, 6, 8-10 and/or 13 elements may be presenton an exterior and/or interior surface of the organosilica material. Forexample, one or more of the Group 1, 2 and/or 13 elements may be presentin a first layer on the organosilica material and one or more of theGroup 6, 8, 9 and/or 10 elements may be present in a second layer, e.g.,at least partially atop the Group 1, 2 and/or 13 elements. Additionallyor alternatively, only one or more Group 6, 8, 9 and/or 10 elements maypresent on an exterior and/or interior surface of the organosilicamaterial. The surface metal(s) can be incorporated into/onto theorganosilica material by any convenient method, such as by impregnation,deposition, grafting, co-condensation, by ion exchange, and/or the like.

II.D. Binder

In various aspects, the adsorbent material may further comprise a binderor be self-bound. Suitable binders, include but are not limited toactive and inactive materials, synthetic or naturally occurringzeolites, as well as inorganic materials such as clays and/or oxidessuch as silica, alumina, zirconia, titania, silica-alumina, ceriumoxide, magnesium oxide, or combinations thereof. In particular, thebinder may be selected from the group consisting of active and inactivematerials, inorganic materials, clays, alumina, silica, silica-alumina,titania, zirconia, or a combination thereof. Particularly, the bindermay be silica-alumina, alumina and/or zirconia, particularly aluminaSilica-alumina may be either naturally occurring or in the form ofgelatinous precipitates or gels including mixtures of silica and metaloxides. It should be noted it is recognized herein that the use of amaterial in conjunction with a zeolite binder material, i.e., combinedtherewith or present during its synthesis, which itself is catalyticallyactive may change the conversion and/or selectivity of the finishedcatalyst. It is also recognized herein that inactive materials cansuitably serve as diluents to control the amount of conversion if thepresent invention is employed in alkylation processes so that alkylationproducts can be obtained economically and orderly without employingother means for controlling the rate of reaction. These inactivematerials may be incorporated into naturally occurring clays, e.g.,bentonite and kaolin, to improve the crush strength of the catalystunder commercial operating conditions and function as binders ormatrices for the catalyst. The adsorbent materials described hereintypically can comprise, in a composited form, a ratio of supportmaterial to binder material of about 100 parts support material to aboutzero parts binder material; about 99 parts support material to about 1parts binder material; about 95 parts support material to about 5 partsbinder material. Additionally or alternatively, the adsorbent materialsdescribed herein typically can comprise, in a composited form, a ratioof support material to binder material ranging from about 90 partssupport material to about 10 parts binder material to about 10 partssupport material to about 90 parts binder material; about 85 partssupport material to about 15 parts binder material to about 15 partssupport material to about 85 parts binder material; about 80 partssupport material to 20 parts binder material to 20 parts supportmaterial to 80 parts binder material, all ratios being by weight,typically from 80:20 to 50:50 support material:binder material,preferably from 65:35 to 35:65. Compositing may be done by conventionalmeans including mulling the materials together followed by extrusion ofpelletizing into the desired finished adsorbent material particles.

III. METHODS OF MAKING THE ADSORBENT MATERIALS

In another embodiment, methods of producing the adsorbent materialsdescribed herein are provided. The method comprises (a) impregnating aporous material support as described herein with a metal (e.g. Group 7,8, 12 and 13 metal ion) as described herein; and (b) drying theimpregnated porous material support.

In various aspects, impregnating the porous material support can beaccomplished by applying an aqueous solution of the metal (e.g. Group 7,8, 12 and 13 metal ion) onto the porous material support. For example,an aqueous solution of the metal (e.g. Group 7, 8, 12 and 13 metal ion)can be sprayed onto the porous material support, e.g., by double-coneimpregnators, or alternatively, by incipient wetness impregnation. Theporous material may be an organosilica material described herein and/oranother siliceous material (e.g., amorphous silica, silica gel, MCM-41)as described herein. Additionally or alternatively, the porous materialdescribed herein may comprise the metal (e.g. Group 7, 8, 12 and 13metal ion) in the amounts described herein (e.g., about 0.5 wt. % toabout 30 wt. %, about 1.0 wt. % to about 15 wt. %). The metal (e.g.Group 7, 8, 12 and 13 metal ion) may be provided by a metal salt (e.g.,a Group 7, 8, 12 and 13 metal salt) which has been dissolved in water ora metal oxide (e.g., a Group 7, 8, 12 and 13 metal oxide). Examples ofmetal salts include, but are not limited to, metal (e.g., Group 7, 8, 12and 13 metal) halides, metal (e.g., Group 7, 8, 12 and 13 metal)sulfates, and metal (e.g Group 7, 8, 12 and 13 metal) phosphates.Particular metal salts include any Fe(II) (Fe²) or Fe(III) (Fe³⁺) salt,such as but not limited to, FeBr₂, FeBr₃, FeCl₃, FeCl₂, Fe₂(SO₄)₃,FeSO₄, FePO₄, and Fe₃(PO₄)₂, particularly, FeCl₃ and FeCl₂. Additionalmetal salts include, but are not limited to, MnBr₂, MnCl₂, MnF₂, MnI₂,ZnBr₂, ZnCl₂, Zn(PO₄)₂, AlCl₃, Al₂(SO₄)₃, AlBr₃, AlF₃ and combinationsthereof. Examples of metal oxides, include but are not limited to,Fe₂O₃, FeO, MnO, Mn₂O₃, ZnO, Al₂O₃, and combinations thereof.

In various aspects, drying of the impregnated porous material can be inthe presence of an inert gas (e.g., nitrogen, argon, etc.) or undervacuum. The impregnated porous material can be dried at a temperature ofat least about 70° C., at least about 80° C., at least about 90° C., atleast about 100° C., at least about 110° C., at least about 120° C., atleast about 130° C., at least about 140° C., at least about 150° C., atleast about 160° C., at least about 170° C., at least about 180° C., atleast about 190° C., or at least about 200° C.

Additionally or alternatively, the impregnated porous material can bedried at a temperature of at about 70° C. to about 200° C., about 70° C.to about 190° C., about 70° C. to about 180° C., about 70° C. to about170° C., about 70° C. to about 160° C., about 70° C. to about 150° C.,about 70° C. to about 140° C., about 70° C. to about 130° C., about 70°C. to about 120° C., about 70° C. to about 110° C., about 70° C. toabout 100° C., about 70° C. to about 90° C., about 70° C. to about 80°C., about 80° C. to about 200° C., about 80° C. to about 190° C., about80° C. to about 180° C., about 80° C. to about 170° C., about 80° C. toabout 160° C., about 80° C. to about 150° C., about 80° C. to about 140°C., about 80° C. to about 130° C., about 80° C. to about 120° C., about80° C. to about 110° C., about 80° C. to about 100° C., about 80° C. toabout 90° C., about 90° C. to about 200° C., about 90° C. to about 190°C., about 90° C. to about 180° C., about 90° C. to about 170° C., about90° C. to about 160° C., about 90° C. to about 150° C., about 90° C. toabout 140° C., about 90° C. to about 130° C., about 90° C. to about 120°C., about 90° C. to about 110° C., about 90° C. to about 100° C., about100° C. to about 200° C., about 100° C. to about 190° C., about 100° C.to about 180° C., about 100° C. to about 170° C., about 100° C. to about160° C., about 100° C. to about 150° C., about 100° C. to about 140° C.,about 100° C. to about 130° C., about 100° C. to about 120° C., about100° C. to about 110° C., about 110° C. to about 200° C., about 110° C.to about 190° C., about 110° C. to about 180° C., about 110° C. to about170° C., about 110° C. to about 160° C., about 110° C. to about 150° C.,about 110° C. to about 140° C., about 110° C. to about 130° C., or about110° C. to about 120° C.

In particular, the impregnated porous material can be dried at atemperature of at about 70° C. to about 200° C., about 80° C. to about160° C., about 90° C. to about 150° C., about 90° C. to about 130° C. orabout 100° C. to about 130° C.

III.A. Methods of Making the Organosilica Materials

In various aspects, methods of making the organosilica materials whichcan be used in the porous adsorbent material are also provided herein.The method of making the organosilica material can comprise (a) addingat least one compound of Formula [Z¹⁵Z¹⁶SiCH₂]₃ (VIII) into the aqueousmixture to form a solution, wherein each Z¹⁵ can be a C₁-C₄ alkoxy groupand Z¹⁶ can be a C₁-C₄ alkoxy group or a C₁-C₄ alkyl group; (b) agingthe solution to produce a pre-product; and (c) drying the pre-product toobtain an organosilica material support which is a polymer comprisingindependent units of a monomer of Formula [Z¹OZ²OSiCH₂]₃ (I), asdescribed herein.

1. Aqueous Mixture

The organosilica materials described herein may be made usingessentially no structure directing agent or porogen. Thus, the aqueousmixture contains essentially no added structure directing agent and/orno added porogen.

As used herein, “no added structure directing agent,” and “no addedporogen” means either (i) there is no component present in the synthesisof the organosilica material that aids in and/or guides thepolymerization and/or polycondensing and/or organization of the buildingblocks that form the framework of the organosilica material; or (ii)such component is present in the synthesis of the organosilica materialin a minor, or a non-substantial, or a negligible amount such that thecomponent cannot be said to aid in and/or guide the polymerizationand/or polycondensing and/or organization of the building blocks thatform the framework of the organosilica material. Further, “no addedstructure directing agent” is synonymous with “no added template” and“no added templating agent.”

A. Structure Directing Agent

Examples of a structure directing agent can include, but are not limitedto, non-ionic surfactants, ionic surfactants, cationic surfactants,silicon surfactants, amphoteric surfactants, polyalkylene oxidesurfactants, fluorosurfactants, colloidal crystals, polymers, hyperbranched molecules, star-shaped molecules, macromolecules, dendrimers,and combinations thereof. Additionally or alternatively, the surfacedirecting agent can comprise or be a poloxamer, a triblock polymer, atetraalkylammonium salt, a nonionic polyoxyethylene alkyl, a Geminisurfactant, or a mixture thereof. Examples of a tetraalkylammonium saltcan include, but are not limited to, cetyltrimethylammonium halides,such as cetyltrimethylammonium chloride (CTAC), cetyltrimethylammoniumbromide (CTAB), and octadecyltrimethylammonium chloride. Other exemplarysurface directing agents can additionally or alternatively includehexadecyltrimethylammonium chloride and/or cetylpyridinium bromide.

Poloxamers are block copolymers of ethylene oxide and propylene oxide,more particularly nonionic triblock copolymers composed of a centralhydrophobic chain of polyoxypropylene (poly(propylene oxide)) flanked bytwo hydrophilic chains of polyoxyethylene (poly(ethylene oxide)).Specifically, the term “poloxamer” refers to a polymer having theformula HO(C₂H₄))a(C₃H₆O)_(b)(C₂H₄O)_(a)H in which “a” and “b” denotethe number of polyoxyethylene and polyoxypropylene units, respectively.Poloxamers are also known by the trade name Pluronic®, for examplePluronic® 123 and Pluronic® F127. An additional triblock polymer isB50-6600.

Nonionic polyoxyethylene alkyl ethers are known by the trade name Brij®,for example Brij® 56, Brij® 58, Brij® 76, Brij® 78. Gemini surfactantsare compounds having at least two hydrophobic groups and at least one oroptionally two hydrophilic groups per molecule have been introduced.

B. Porogen

A porogen material is capable of forming domains, discrete regions,voids and/or pores in the organosilica material. An example of a porogenis a block copolymer (e.g., a di-block polymer). As used herein, porogendoes not include water. Examples of polymer porogens can include, butare not limited to, polyvinyl aromatics, such as polystyrenes,polyvinylpyridines, hydrogenated polyvinyl aromatics,polyacrylonitriles, polyalkylene oxides, such as polyethylene oxides andpolypropylene oxides, polyethylenes, polylactic acids, polysiloxanes,polycaprolactones, polycaprolactams, polyurethanes, polymethacrylates,such as polymethylmethacrylate or polymethacrylic acid, polyacrylates,such as polymethylacrylate and polyacrylic acid, polydienes such aspolybutadienes and polyisoprenes, polyvinyl chlorides, polyacetals, andamine-capped alkylene oxides, as well as combinations thereof.

Additionally or alternatively, porogens can be thermoplastichomopolymers and random (as opposed to block) copolymers. As usedherein, “homopolymer” means compounds comprising repeating units from asingle monomer. Suitable thermoplastic materials can include, but arenot limited to, homopolymers or copolymers of polystyrenes,polyacrylates, polymethacrylates, polybutadienes, polyisoprenes,polyphenylene oxides, polypropylene oxides, polyethylene oxides,poly(dimethylsiloxanes), polytetrahydrofurans, polyethylenes,polycyclohexylethylenes, polyethyloxazolines, polyvinylpyridines,polycaprolactones, polylactic acids, copolymers of these materials andmixtures of these materials. Examples of polystyrene include, but arenot limited to anionic polymerized polystyrene, syndiotacticpolystyrene, unsubstituted and substituted polystyrenes (for example,poly(α-methyl styrene)). The thermoplastic materials may be linear,branched, hyperbranched, dendritic, or star like in nature.

Additionally or alternatively, the porogen can be a solvent. Examples ofsolvents can include, but are not limited to, ketones (e.g.,cyclohexanone, cyclopentanone, 2-heptanone, cycloheptanone,cyclooctanone, cyclohexylpyrrolidinone, methyl isobutyl ketone, methylethyl ketone, acetone), carbonate compounds (e.g., ethylene carbonate,propylene carbonate), heterocyclic compounds (e.g.,3-methyl-2-oxazolidinone, dimethylimidazolidinone, N-methylpyrrolidone,pyridine), cyclic ethers (e dioxane, tetrahydrofuran), chain ethers(e.g., diethyl ether, ethylene glycol dimethyl ether, propylene glycoldimethyl ether, tetraethylene glycol dimethyl ether, polyethylene glycoldimethyl ether, ethylene glycol monomethyl ether, ethylene glycolmonoethyl ether, propylene glycol monomethyl ether (PGME), triethyleneglycol monobutyl ether, propylene glycol monopropyl ether, triethyleneglycol monomethyl ether, diethylene glycol ethyl ether, diethyleneglycol methyl ether, dipropylene glycol methyl ether, dipropylene glycoldimethyl ether, propylene glycol phenyl ether, tripropylene glycolmethyl ether), alcohols (e.g., methanol, ethanol), polyhydric alcohols(e.g., ethylene glycol, propylene glycol, polyethylene glycol,polypropylene glycol, glycerin, dipropylene glycol), nitrile compounds(e.g., acetonitrile, glutarodinitrile, methoxyacetonitrile,propionitrile, benzonitrile), esters (e.g., ethyl acetate, butylacetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethylethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate,2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate,propylene glycol monomethyl ether acetate (PGMEA), butyrolactone,phosphoric acid ester, phosphonic acid ester), aprotic polar substances(e.g., dimethyl sulfoxide, sulfolane, dimethylformamide,dimethylacetamide), nonpolar solvents (e.g., toluene, xylene,mesitylene), chlorine-based solvents (e.g., methylene dichloride,ethylene dichloride), benzene, dichlorobenzene, naphthalene, diphenylether, diisopropylbenzene, triethylamine, methyl benzoate, ethylbenzoate, butyl benzoate, monomethyl ether acetate hydroxy ethers suchas dibenzylethers, diglyme, triglyme, and mixtures thereof.

C. Base/Acid

In various embodiments, the aqueous mixture used in methods providedherein can comprise a base and/or an acid.

In certain embodiments where the aqueous mixture comprises a base, theaqueous mixture can have a pH from about 8 to about 15, from about 8 toabout 14.5, from about 8 to about 14, from about 8 to about 13.5, fromabout 8 to about 13, from about 8 to about 12.5, from about 8 to about12, from about 8 to about 11.5, from about 8 to about 11, from about 8to about 10.5, from about 8 to about 10, from about 8 to about 9.5, fromabout 8 to about 9, from about 8 to about 8.5, from about 8.5 to about15, from about 8.5 to about 14.5, from about 8.5 to about 14, from about8.5 to about 13.5, from about 8.5 to about 13, from about 8.5 to about12.5, from about 8.5 to about 12, from about 8.5 to about 11.5, fromabout 8.5 to about 11, from about 8.5 to about 10.5, from about 8.5 toabout 10, from about 8.5 to about 9.5, from about 8.5 to about 9, fromabout 9 to about 15, from about 9 to about 14.5, from about 9 to about14, from about 9 to about 13.5, from about 9 to about 13, from about 9to about 12.5, from about 9 to about 12, from about 9 to about 11.5,from about 9 to about 11, from about 9 to about 10.5, from about 9 toabout 10, from about 9 to about 9.5, from about 9.5 to about 15, fromabout 9.5 to about 14.5, from about 9.5 to about 14, from about 9.5 toabout 13.5, from about 9.5 to about 13, from about 9.5 to about 12.5,from about 9.5 to about 12, from about 9.5 to about 11.5, from about 9.5to about 11, from about 9.5 to about 10.5, from about 9.5 to about 10,from about 10 to about 15, from about 10 to about 14.5, from about 10 toabout 14, from about 10 to about 13.5, from about 10 to about 13, fromabout 10 to about 12.5, from about 10 to about 12, from about 10 toabout 11.5, from about 10 to about 11, from about 10 to about 10.5, fromabout 10.5 to about 15, from about 10.5 to about 14.5, from about 10.5to about 14, from about 10.5 to about 13.5, from about 10.5 to about 13,from about 10.5 to about 12.5, from about 10.5 to about 12, from about10.5 to about 11.5, from about 10.5 to about 11, from about 11 to about15, from about 11 to about 14.5, from about 11 to about 14, from about11 to about 13.5, from about 11 to about 13, from about 11 to about12.5, from about 11 to about 12, from about 11 to about 11.5, from about11.5 to about 15, from about 11.5 to about 14.5, from about 11.5 toabout 14, from about 11.5 to about 13.5, from about 11.5 to about 13,from about 11.5 to about 12.5, from about 11.5 to about 12, from about12 to about 15, from about 12 to about 14.5, from about 12 to about 14,from about 12 to about 13.5, from about 12 to about 13, from about 12 toabout 12.5, from about 12.5 to about 15, from about 12.5 to about 14.5,from about 12.5 to about 14, from about 12.5 to about 13.5, from about12.5 to about 13, from about 12.5 to about 15, from about 12.5 to about14.5, from about 12.5 to about 14, from about 12.5 to about 13.5, fromabout 12.5 to about 13, from about 13 to about 15, from about 13 toabout 14.5, from about 13 to about 14, from about 13 to about 13.5, fromabout 13.5 to about 15, from about 13.5 to about 14.5, from about 13.5to about 14, from about 14 to about 15, from about 14 to about 14.5, andfrom about 14.5 to about 15.

In a particular embodiment comprising a base, the pH can be from about 9to about 15, from about 9 to about 14 or about 8 to about 14.

Exemplary bases can include, but are not limited to, sodium hydroxide,potassium hydroxide, lithium hydroxide, pyridine, pyrrole, piperazine,pyrrolidine, piperidine, picoline, monoethanolamine, diethanolamine,dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine,diazabicyclooctane, diazabicyclononane, diazabicycloundecene,tetramethylammonium hydroxide, tetraethylammonium hydroxide,tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ammonia,ammonium hydroxide, methylamine, ethylamine, propylamine, butylamine,pentylamine, hexylamine, octylamine, nonylamine, decylamine,N,N-dimethylamine, N,N-diethylamine, N,N-dipropylamine,N,N-dibutylamine, trimethylamine, triethylamine, tripropylamine,tributylamine, cyclohexylamine, trimethylimidine,1-amino-3-methylbutane, dimethylglycine, 3-amino-3-methylamine, and thelike. These bases may be used either singly or in combination. In aparticular embodiment, the base can comprise or be sodium hydroxideand/or ammonium hydroxide.

In certain embodiments where the aqueous mixture comprises an acid, theaqueous mixture can have a pH from about 0.01 to about 6.0, from about0.01 to about 5, from about 0.01 to about 4, from about 0.01 to about 3,from about 0.01 to about 2, from about 0.01 to about 1, 0.1 to about6.0, about 0.1 to about 5.5, about 0.1 to about 5.0, from about 0.1 toabout 4.8, from about 0.1 to about 4.5, from about 0.1 to about 4.2,from about 0.1 to about 4.0, from about 0.1 to about 3.8, from about 0.1to about 3.5, from about 0.1 to about 3.2, from about 0.1 to about 3.0,from about 0.1 to about 2.8, from about 0.1 to about 2.5, from about 0.1to about 2.2, from about 0.1 to about 2.0, from about 0.1 to about 1.8,from about 0.1 to about 1.5, from about 0.1 to about 1.2, from about 0.1to about 1.0, from about 0.1 to about 0.8, from about 0.1 to about 0.5,from about 0.1 to about 0.2, about 0.2 to about 6.0, about 0.2 to about5.5, from about 0.2 to about 5, from about 0.2 to about 4.8, from about0.2 to about 4.5, from about 0.2 to about 4.2, from about 0.2 to about4.0, from about 0.2 to about 3.8, from about 0.2 to about 3.5, fromabout 0.2 to about 3.2, from about 0.2 to about 3.0, from about 0.2 toabout 2.8, from about 0.2 to about 2.5, from about 0.2 to about 2.2,from about 0.2 to about 2.0, from about 0.2 to about 1.8, from about 0.2to about 1.5, from about 0.2 to about 1.2, from about 0.2 to about 1.0,from about 0.2 to about 0.8, from about 0.2 to about 0.5, about 0.5 toabout 6.0, about 0.5 to about 5.5, from about 0.5 to about 5, from about0.5 to about 4.8, from about 0.5 to about 4.5, from about 0.5 to about4.2, from about 0.5 to about 4.0, from about 0.5 to about 3.8, fromabout 0.5 to about 3.5, from about 0.5 to about 3.2, from about 0.5 toabout 3.0, from about 0.5 to about 2.8, from about 0.5 to about 2.5,from about 0.5 to about 2.2, from about 0.5 to about 2.0, from about 0.5to about 1.8, from about 0.5 to about 1.5, from about 0.5 to about 1.2,from about 0.5 to about 1.0, from about 0.5 to about 0.8, about 0.8 toabout 6.0, about 0.8 to about 5.5, from about 0.8 to about 5, from about0.8 to about 4.8, from about 0.8 to about 4.5, from about 0.8 to about4.2, from about 0.8 to about 4.0, from about 0.8 to about 3.8, fromabout 0.8 to about 3.5, from about 0.8 to about 3.2, from about 0.8 toabout 3.0, from about 0.8 to about 2.8, from about 0.8 to about 2.5,from about 0.8 to about 2.2, from about 0.8 to about 2.0, from about 0.8to about 1.8, from about 0.8 to about 1.5, from about 0.8 to about 1.2,from about 0.8 to about 1.0, about 1.0 to about 6.0, about 1.0 to about5.5, from about 1.0 to about 5.0, from about 1.0 to about 4.8, fromabout 1.0 to about 4.5, from about 1.0 to about 4.2, from about 1.0 toabout 4.0, from about 1.0 to about 3.8, from about 1.0 to about 3.5,from about 1.0 to about 3.2, from about 1.0 to about 3.0, from about 1.0to about 2.8, from about 1.0 to about 2.5, from about 1.0 to about 2.2,from about 1.0 to about 2.0, from about 1.0 to about 1.8, from about 1.0to about 1.5, from about 1.0 to about 1.2, about 1.2 to about 6.0, about1.2 to about 5.5, from about 1.2 to about 5.0, from about 1.2 to about4.8, from about 1.2 to about 4.5, from about 1.2 to about 4.2, fromabout 1.2 to about 4.0, from about 1.2 to about 3.8, from about 1.2 toabout 3.5, from about 1.2 to about 3.2, from about 1.2 to about 3.0,from about 1.2 to about 2.8, from about 1.2 to about 2.5, from about 1.2to about 2.2, from about 1.2 to about 2.0, from about 1.2 to about 1.8,from about 1.2 to about 1.5, about 1.5 to about 6.0, about 1.5 to about5.5, from about 1.5 to about 5.0, from about 1.5 to about 4.8, fromabout 1.5 to about 4.5, from about 1.5 to about 4.2, from about 1.5 toabout 4.0, from about 1.5 to about 3.8, from about 1.5 to about 3.5,from about 1.5 to about 3.2, from about 1.5 to about 3.0, from about 1.5to about 2.8, from about 1.5 to about 2.5, from about 1.5 to about 2.2,from about 1.5 to about 2.0, from about 1.5 to about 1.8, about 1.8 toabout 6.0, about 1.8 to about 5.5, from about 1.8 to about 5.0, fromabout 1.8 to about 4.8, from about 1.8 to about 4.5, from about 1.8 toabout 4.2, from about 1.8 to about 4.0, from about 1.8 to about 3.8,from about 1.8 to about 3.5, from about 1.8 to about 3.2, from about 1.8to about 3.0, from about 1.8 to about 2.8, from about 1.8 to about 2.5,from about 1.8 to about 2.2, from about 1.8 to about 2.0, about 2.0 toabout 6.0, about 2.0 to about 5.5, from about 2.0 to about 5.0, fromabout 2.0 to about 4.8, from about 2.0 to about 4.5, from about 2.0 toabout 4.2, from about 2.0 to about 4.0, from about 2.0 to about 3.8,from about 2.0 to about 3.5, from about 2.0 to about 3.2, from about 2.0to about 3.0, from about 2.0 to about 2.8, from about 2.0 to about 2.5,from about 2.0 to about 2.2, about 2.2 to about 6.0, about 2.2 to about5.5, from about 2.2 to about 5.0, from about 2.2 to about 4.8, fromabout 2.2 to about 4.5, from about 2.2 to about 4.2, from about 2.2 toabout 4.0, from about 2.2 to about 3.8, from about 2.2 to about 3.5,from about 2.2 to about 3.2, from about 2.2 to about 3.0, from about 2.2to about 2.8, from about 2.2 to about 2.5, about 2.5 to about 6.0, about2.5 to about 5.5, from about 2.5 to about 5.0, from about 2.5 to about4.8, from about 2.5 to about 4.5, from about 2.5 to about 4.2, fromabout 2.5 to about 4.0, from about 2.5 to about 3.8, from about 2.5 toabout 3.5, from about 2.5 to about 3.2, from about 2.5 to about 3.0,from about 2.5 to about 2.8, from about 2.8 to about 6.0, about 2.8 toabout 5.5, from about 2.8 to about 5.0, from about 2.8 to about 4.8,from about 2.8 to about 4.5, from about 2.8 to about 4.2, from about 2.8to about 4.0, from about 2.8 to about 3.8, from about 2.8 to about 3.5,from about 2.8 to about 3.2, from about 2.8 to about 3.0, from about 3.0to about 6.0, from about 3.5 to about 5.5, from about 3.0 to about 5.0,from about 3.0 to about 4.8, from about 3.0 to about 4.5, from about 3.0to about 4.2, from about 3.0 to about 4.0, from about 3.0 to about 3.8,from about 3.0 to about 3.5, from about 3.0 to about 3.2, from about 3.2to about 6.0, from about 3.2 to about 5.5, from about 3.2 to about 5,from about 3.2 to about 4.8, from about 3.2 to about 4.5, from about 3.2to about 4.2, from about 3.2 to about 4.0, from about 3.2 to about 3.8,from about 3.2 to about 3.5, from about 3.5 to about 6.0, from about 3.5to about 5.5, from about 3.5 to about 5, from about 3.5 to about 4.8,from about 3.5 to about 4.5, from about 3.5 to about 4.2, from about 3.5to about 4.0, from about 3.5 to about 3.8, from about 3.8 to about 5,from about 3.8 to about 4.8, from about 3.8 to about 4.5, from about 3.8to about 4.2, from about 3.8 to about 4.0, from about 4.0 to about 6.0,from about 4.0 to about 5.5, from about 4.0 to about 5, from about 4.0to about 4.8, from about 4.0 to about 4.5, from about 4.0 to about 4.2,from about 4.2 to about 5, from about 4.2 to about 4.8, from about 4.2to about 4.5, from about 4.5 to about 5, from about 4.5 to about 4.8, orfrom about 4.8 to about 5.

In a particular embodiment comprising an acid, the pH can be from about0.01 to about 6.0, 0.2 to about 6.0, about 0.2 to about 5.0 or about 0.2to about 4.5.

Exemplary acids can include, but are not limited to, inorganic acidssuch as hydrochloric acid, nitric acid, sulfuric acid, hydrofluoricacid, phosphoric acid, boric acid and oxalic acid; and organic acidssuch as acetic acid, propionic acid, butanoic acid, pentanoic acid,hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoicacid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacicacid, gallic acid, butyric acid, mellitic acid, arachidonic acid,shikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleicacid, linolenic acid, salicylic acid, benzoic acid, p-amino-benzoicacid, p-toluenesulfonic acid, benzenesulfonic acid, monochloroaceticacid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid,formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid,citric acid, tartaric acid, succinic acid, itaconic acid, mesaconicacid, citraconic acid, malic acid, a hydrolysate of glutaric acid, ahydrolysate of maleic anhydride, a hydrolysate of phthalic anhydride,and the like. These acids may be used either singly or in combination.In a particular embodiment, the acid can comprise or be hydrochloricacid.

2. Compounds of Formula (VIII)

In certain embodiments, the methods provided herein can comprise thestep of adding at least one compound of Formula [Z¹⁵Z¹⁶SiCH₂]₃ (VIII)into the aqueous mixture to form a solution, wherein each Z¹⁵ can be aC₁-C₄ alkoxy group and each Z¹⁶ can be a C₁-C₄ alkoxy group or a C₁-C₄alkyl group.

In one embodiment, each Z¹⁵ can be a C₁-C₃ alkoxy or methoxy or ethoxy.

Additionally or alternatively, each Z¹⁶ can be a C₁-C₄ alkoxy, a C₁-C₃alkoxy or methoxy or ethoxy. Additionally or alternatively, each Z¹⁶ cancomprise methyl, ethyl or propyl, such as a methyl or ethyl.

Additionally or alternatively, each Z¹⁵ can be a C₁-C₂ alkoxy group andZ¹⁶ can be a C₁-C₂ alkoxy group or a C₁-C₂ alkyl group.

Additionally or alternatively, each Z¹⁵ can be methoxy or ethoxy andeach Z¹⁶ can be methyl or ethyl.

In a particular embodiment, Z¹⁵ and Z¹⁶ can be ethoxy, such that thecompound corresponding to Formula (VIII) can be1,1,3,3,5,5-hexaethoxy-1,3,5-trisilacyclohexane, ([(EtO)₂SiCH₂]₃).

In a particular embodiment, Z¹⁵ can be ethoxy and Z¹⁶ can be methyl,such that compound corresponding to Formula (VIII) can be1,3,5-trimethyl-1,3,5-triethoxy-1,3,5-trisilacyclohexane, ([EtOCH₃SiCH₂]₃).

Additionally or alternatively, the method can further comprise adding tothe aqueous mixture a further compound of Formula (VIII), which may bethe same or different. In the case where different compounds of Formula(VIII) are added, an organosilica material support can be obtained whichis a copolymer comprising at least one independent unit of Formula (I)as described herein and at least one independent unit of Formula (II) asdescribed herein. For example,1,1,3,3,5,5-hexaethoxy-1,3,5-trisilacyclohexane, ([(EtO)₂SiCH₂]₃) and1,3,5-trimethyl-1,3,5-triethoxy-1,3,5-trisilacyclohexane, ([EtOCH₃SiCH₂]₃) may be added to the aqueous mixture.

When more than one compound of Formula (VIII) is used, the respectivecompounds may be used in a wide variety of molar ratios. For example, iftwo compounds of Formula (VIII) are used, the molar ratio of eachcompound may vary from 1:99 to 99:1, such as from 10:90 to 90:10. Theuse of different compounds of Formula (VIII) allows to tailor theproperties of the organosilica materials made by the process of theinvention, as will be further explained in the examples and in thesection of this specification describing the properties of theorganosilicas made by the present processes.

3. Compounds of Formula (IX)

In additional embodiments, the methods provided herein can furthercomprise adding to the aqueous solution a compound of FormulaZ¹⁷OZ¹⁸Z¹⁹Z²⁰Si (VIII) to obtain an organosilica material which is acopolymer comprising at least one independent unit of Formula (I) asdescribed herein, at least one independent unit of Formula (III) asdescribed herein and optionally at least one independent unit of Formula(II) as described herein, wherein each Z¹⁷ can be a C₁-C₆ alkyl group,and Z¹⁸, Z¹⁹ and Z²⁰ each independently can be selected from the groupconsisting of a C₁-C₆ alkyl group, a C₁-C₆ alkoxy group, anitrogen-containing C₁-C₁₀ alkyl group, a nitrogen-containingheteroaralkyl group, and a nitrogen-containing optionally substitutedheterocycloalkyl group.

Additionally or alternatively, each Z¹⁷ can be a C₁-C₆ alkyl group, andZ¹⁸, Z¹⁹ and Z²⁰ each independently can be selected from the groupconsisting of a C₁-C₆ alkyl group and a C₁-C₆ alkoxy group. Additionallyor alternatively, Z¹⁸, Z¹⁹ and Z²⁰ each independently optionally can bea nitrogen-containing C₁-C₁₀ alkyl group, a nitrogen-containingheteroaralkyl group, and a nitrogen-containing optionally substitutedheterocycloalkyl group.

In various aspects, each Z¹⁷ can be a C₁-C₅ alkyl group, a C₁-C₄ alkylgroup, a C₁-C₃ alkyl group, a C₁-C₂ alkyl group, or methyl. Inparticular, Z¹⁷ can be methyl or ethyl.

Additionally or alternatively, Z¹⁸, Z¹⁹ and Z²⁰ can be eachindependently a C₁-C₅ alkyl group, a C₁-C₄ alkyl group, a C₁-C₃ alkylgroup, a C₁-C₂ alkyl group, or methyl.

Additionally or alternatively, each Z¹⁷ can be a C₁-C₂ alkyl group andZ¹⁸, Z¹⁹ and Z²⁰ can be each independently a C₁-C₂ alkyl group.

Additionally or alternatively, Z¹⁸, Z¹⁹ and Z²⁰ can be eachindependently a C₁-C₅ alkoxy group, a C₁-C₄ alkoxy group, a C₁-C₃ alkoxygroup, a C₁-C₂ alkoxy group, or methoxy.

Additionally or alternatively, each Z¹⁷ can be a C₁-C₂ alkyl group andZ¹⁸, Z¹⁹ and Z²⁰ can be each independently a C₁-C₂ alkoxy group.

Additionally or alternatively, each Z¹⁷ can be a C₁-C₂ alkyl group andZ¹⁸, Z¹⁹ and Z²⁰ can be each independently a C₁-C₂ alkyl group or aC₁-C₂ alkoxy group.

Additionally or alternatively, Z¹⁸, Z¹⁹ and Z²⁰ can be eachindependently a nitrogen-containing C₁-C₉ alkyl group, anitrogen-containing C₁-C₈ alkyl group, a nitrogen-containing C₁-C₇ alkylgroup, a nitrogen-containing C₁-C₆ alkyl group, a nitrogen-containingC₁-C₅ alkyl group, a nitrogen-containing C₁-C₄ alkyl group, anitrogen-containing C₁-C₃ alkyl group, a nitrogen-containing C₁-C₂ alkylgroup, or a methylamine. In particular, Z¹⁸, Z¹⁹ and Z²⁰ can be eachindependently a nitrogen-containing C₂-C₁₀ alkyl group, anitrogen-containing C₃-C₁₀ alkyl group, a nitrogen-containing C₃-C₉alkyl group, or a nitrogen-containing C₃-C₈ alkyl group. Theaforementioned nitrogen-containing alkyl groups may have one or morenitrogen atoms (e.g., 2, 3, etc.). Examples of nitrogen-containingC₁-C₁₀ alkyl groups include, but are not limited to,

Additionally or alternatively, each Z¹⁷ can be a C₁-C₂ alkyl group andZ¹⁸, Z¹⁹ and Z²⁰ can be each independently a nitrogen-containing C₃-C₈alkyl group.

Additionally or alternatively, each Z¹⁷ can be a C₁-C₂ alkyl group andZ¹⁸, Z¹⁹ and Z²⁰ can be each independently a C₁-C₂ alkyl group, a C₁-C₂alkoxy group or a nitrogen-containing C₃-C₈ alkyl group.

Additionally or alternatively, Z¹⁸, Z¹⁹ and Z²⁰ can be eachindependently a nitrogen-containing heteroaralkyl group. Thenitrogen-containing heteroaralkyl group can be a nitrogen-containingC₄-C₁₂ heteroaralkyl group, a nitrogen-containing C₄-C₁₀ heteroaralkylgroup, or a nitrogen-containing C₄-C₈ heteroaralkyl group. Examples ofnitrogen-containing heteroaralkyl groups include but are not limited topyridinylethyl, pyridinylpropyl, pyridinylmethyl, indolylmethyl,pyrazinylethyl, and pyrazinylpropyl. The aforementionednitrogen-containing heteroaralkyl groups may have one or more nitrogenatoms (e.g., 2, 3, etc.).

Additionally or alternatively, each Z¹⁷ can be a C₁-C₂ alkyl group andZ¹⁸, Z¹⁹ and Z²⁰ can be each independently a nitrogen-containingheteroaralkyl group.

Additionally or alternatively, each Z¹⁷ can be a C₁-C₂ alkyl group andZ¹⁸, Z¹⁹ and Z²⁰ can be each independently a C₁-C₂ alkyl group, a C₁-C₂alkoxy group, a nitrogen-containing C₃-C₈ alkyl group or anitrogen-containing heteroaralkyl group.

Additionally or alternatively, Z¹⁸, Z¹⁹ and Z²⁰ can be eachindependently a nitrogen-containing heterocycloalkyl group, wherein theheterocycloalkyl group may be optionally substituted with a C₁-C₆ alkylgroup, particularly a C₁-C₄ alkyl group. The nitrogen-containingheterocycloalkyl group can be a nitrogen-containing C₄-C₁₂heterocycloalkyl group, a nitrogen-containing C₄-C₁₀ heterocycloalkylgroup, or a nitrogen-containing C₄-C₈ heterocycloalkyl group. Examplesof nitrogen-containing heterocycloalkyl groups include but are notlimited to piperazinylethyl, piperazinylpropyl, piperidinylethyl,piperidinylpropyl. The aforementioned nitrogen-containingheterocycloalkyl groups may have one or more nitrogen atoms (e.g., 2, 3,etc.).

Additionally or alternatively, each Z¹⁷ can be a C₁-C₂ alkyl group andZ¹⁸, Z¹⁹ and Z²⁰ can be each independently a nitrogen-containingoptionally substituted heterocycloalkyl group.

Additionally or alternatively, each Z¹⁷ can be a C₁-C₂ alkyl group andZ¹⁸, Z¹⁹ and Z²⁰ can be each independently a C₁-C₂ alkyl group, a C₁-C₂alkoxy group, a nitrogen-containing C₃-C₈ alkyl group, anitrogen-containing heteroaralkyl group, or a nitrogen-containingoptionally substituted heterocycloalkyl group.

Additionally or alternatively, each Z¹⁷ can be a C₁-C₂ alkyl group andZ¹⁸, Z¹⁹ and Z²⁰ can be each independently a C₁-C₂ alkyl group, C₁-C₂alkoxy group, a nitrogen-containing C₃-C₁₀ alkyl group, anitrogen-containing C₄-C₁₀ heteroaralkyl group, or a nitrogen-containingoptionally substituted C₄-C₁₀ heterocycloalkyl group.

In a particular embodiment, Z¹⁷ can be ethyl and Z¹⁸, Z¹⁹ and Z²⁰ can beethoxy, such that the compound corresponding to Formula (IX) can betetraethyl orthosilicate (TEOS) ((EtO)₄Si).

In another particular embodiment, a compound of Formula (VIII) can be1,1,3,3,5,5-hexaethoxy-1,3,5-trisilacyclohexane ([(EtO)₂SiCH₂]₃) and acompound of Formula (IX) can be tetraethyl orthosilicate (TEOS)((EtO)₄Si).

In another particular embodiment, Z¹⁷ can be ethyl, Z¹⁸ can be methyland Z¹⁹ and Z²⁰ can be ethoxy, such that the compound corresponding toFormula (IX) can be methyltriethoxysilane (MTES) ((EtO)₃ CH₃Si).

In another particular embodiment, a compound of Formula (VIII) can be1,1,3,3,5,5-hexaethoxy-1,3,5-trisilacyclohexane ([(EtO)₂SiCH₂]₃) and acompound of Formula (IX) can be methyltriethoxysilane (MTES)((EtO)₃CH₃—Si).

In another particular embodiment, a compound of Formula (VIII) can be1,3,5-trimethyl-1,3,5-triethoxy-1,3,5-trisilacyclohexane ([EtOCH₃SiCH₂]₃ and a compound of Formula (IX) can be tetraethyl orthosilicate(TEOS) ((EtO)₄ Si).

In another particular embodiment, Z¹⁷ can be ethyl, Z¹⁸ and Z¹⁹ can beethoxy and Z²⁰ can be

such that the compound corresponding to Formula (IX) can be(3-aminopropyl)triethoxysilane (H₂N(CH₂)₃(EtO)₃Si).

In another particular embodiment, a compound of Formula (VIII) can be1,1,3,3,5,5-hexaethoxy-1,3,5-trisilacyclohexane ([(EtO)₂SiCH₂]₃) and acompound of Formula (IX) can be (3-aminopropyl)triethoxysilane(H₂N(CH₂)₃(EtO)₃Si).

In another particular embodiment, Z¹⁷ can be methyl, Z¹⁸ and Z¹⁹ can bemethoxy and Z²⁰ can be

such that the compound corresponding to Formula (IX) can be(N,N-dimethylaminopropyl)trimethoxysilane (((CH₃)₂N(CH₂)₃)(MeO)₃Si).

In another particular embodiment, a compound of Formula (VIII) can be1,1,3,3,5,5-hexaethoxy-1,3,5-trisilacyclohexane ([(EtO)₂SiCH₂]₃) and acompound of Formula (IX) can be(N,N-dimethylaminopropyl)trimethoxysilane (((CH₃)₂N(CH₂)₃)(MeO)₃Si).

In another particular embodiment, Z¹⁷ can be ethyl, Z¹⁸ and Z¹⁹ can beethoxy and Z²⁰ can be

such that the compound corresponding to Formula (IX) can be(N-(2-aminoethyl)-3-aminopropyltriethoxysilane((H₂N(CH₂)₂NH(CH₂)₃)(EtO)₂Si).

In another particular embodiment, a compound of Formula (VIII) can be1,1,3,3,5,5-hexaethoxy-1,3,5-trisilacyclohexane ([(EtO)₂SiCH₂]₃) and acompound of Formula (IX) can be(N-(2-aminoethyl)-3-aminopropyltriethoxysilane((H₂N(CH₂)₂NH(CH₂)₃)(EtO)₂Si).

In another particular embodiment, Z¹⁷ can be ethyl, Z¹⁸ and Z¹⁹ can beethoxy and Z²⁰ can be

such that the compound corresponding to Formula (IX) can be4-methyl-1-(3-triethoxysilylpropyl)-piperazine.

In another particular embodiment, a compound of Formula (VII) can be1,1,3,3,5,5-hexaethoxy-1,3,5-trisilacyclohexane ([(EtO)₂SiCH₂]₃) and acompound of Formula (IX) can be4-methyl-1-(3-triethoxysilylpropyl)-piperazine.

In another particular embodiment, Z¹⁷ can be ethyl, Z¹⁸ and Z¹⁹ can beethoxy and Z²⁰ can be

such that the compound corresponding to Formula (IX) can be4-(2-(triethoxysilyl)ethyl)pyridine.

In another particular embodiment, a compound of Formula (VIII) can1,1,3,3,5,5-hexaethoxy-1,3,5-trisilacyclohexane ([(EtO)₂SiCH₂]₃) and acompound of Formula (IX) can be 4-(2-(triethoxysilyl)ethyl)pyridine.

In another particular embodiment, Z¹⁷ can be ethyl, Z¹⁸ and Z¹⁹ can beethoxy and Z²⁰ can be

such that the compound corresponding to Formula (Va) can be1-(3-(triethoxysilyl)propyl)-4,5-dihydro-1H-imidazole.

In another particular embodiment, a compound of Formula (VIII) can be1,1,3,3,5,5-hexaethoxy-1,3,5-trisilacyclohexane ([(EtO)₂SiCH₂]₃) and acompound of Formula (IX) can be1-(3-(triethoxysilyl)propyl)-4,5-dihydro-1H-imidazole.

The molar ratio of compound of Formula (VIII) to compound of Formula(IX) may vary within wide limits, such as from about 99:1 to about 1:99,from about 1:5 to about 5:1, from about 4:1 to about 1:4 or from about3:2 to about 2:3. For example, a molar ratio of compound of Formula(VIII) to compound of Formula (IX) can be from about 4:1 to 1:4 or fromabout 2.5:1 to about 1:2.5, about 2:1 to about 1:2, such as about 1.5:1to about 1.5:1.

4. Compounds of Formula (X)

In additional embodiments, the methods provided herein can furthercomprise adding to the aqueous solution a compound of FormulaZ²¹Z²²Z²³Si—R¹—SiZ²¹Z²³Z²⁴ (X) to obtain an organosilica material whichis a copolymer comprising at least one independent unit Formula (I) asdescribed herein, at least one independent unit of Formula (IV) asdescribed herein and optionally at least one independent unit ofFormulas (II) and/or (III) as described herein, wherein each Z²¹independently can be a C₁-C₄ alkoxy group; Z²² and Z²³ eachindependently can be a C₁-C₄ alkoxy group or a C₁-C₄ alkyl group; andeach R¹ can be selected from the group consisting a C₁-C₈ alkylenegroup, a C₂-C₈ alkenylene group, a C₂-C₈ alkynylene group, anitrogen-containing C₂-C₁₀ alkylene group, an optionally substitutedC₆-C₂₀ aralkyl group, and an optionally substituted C₄-C₂₀heterocycloalkyl group.

Additionally or alternatively, each Z²¹ independently can be a C₁-C₄alkoxy group; Z²² and Z²³ each independently can be a C₁-C₄ alkoxy groupor a C₁-C₄ alkyl group; and each R¹ can be selected from the groupconsisting a C₁-C₈ alkylene group, a C₂-C₈ alkenylene group, and a C₂-C₈alkynylene group. Additionally or alternatively, R¹ can optionally be anitrogen-containing C₁-C₁₀ alkylene group, an optionally substitutedC₆-C₂₀ aralkyl group, and/or an optionally substituted C₄-C₂₀heterocycloalkyl group.

In various embodiments, each Z²¹ can be a C₁-C₃ alkoxy group, a C₁-C₂alkoxy group, or methoxy.

Additionally or alternatively, Z²² and Z²³ each independently can be aC₁-C₃ alkoxy group, a C₁-C₂ alkoxy group, or methoxy.

Additionally or alternatively, each Z²¹ can be a C₁-C₂ alkoxy group andZ²² and Z²³ each independently can be a C₁-C₂ alkoxy group.

Additionally or alternatively, Z²² and Z²³ each independently can be aC₁-C₃ alkyl group, a C₁-C₂ alkyl group, or methyl.

Additionally or alternatively, each Z²¹ can be a C₁-C₂ alkoxy group andZ²² and Z²³ each independently can be a C₁-C₂ alkyl group.

Additionally or alternatively, Z²¹ can be a C₁-C₂ alkoxy group and Z²²and Z²³ each independently can be a C₁-C₂ alkoxy group or a C₁-C₂ alkylgroup.

Additionally or alternatively, each R¹ can be a C₁-C₇ alkylene group, aC₁-C₆ alkylene group, a C₁-C₅ alkylene group, a C₁-C₄ alkylene group, aC₁-C₃ alkylene group, a C₁-C₂ alkylene group, or —CH₂—.

Additionally or alternatively, each Z²¹ can be a C₁-C₂ alkoxy group; Z²²and Z²³ each independently can be a C₁-C₂ alkoxy group or a C₁-C₂ alkylgroup; and each R⁷ can be a C₁-C₂ alkylene group.

Additionally or alternatively, each R¹ can be a C₂-C₇ alkenylene group,a C₁-C₆ alkenylene group, a C₂-C₅ alkenylene group, a C₂-C₄ a alkenylenegroup, a C₂-C₃ alkenylene group, or —CH═CH—.

Additionally or alternatively, each Z²¹ can be a C₁-C₂ alkoxy group; Z²²and Z²³ each independently can be a C₁-C₂ alkoxy group or a C₁-C₂ alkylgroup; and each R¹ can be a C₁-C₂ alkenylene group.

Additionally or alternatively, each Z²¹ can be a C₁-C₂ alkoxy group; Z²²and Z²³ each independently can be a C₁-C₂ alkoxy group or a C₁-C₂ alkylgroup; and each R¹ can be a C₁-C₂ alkylene group or a C₁-C₂ alkenylenegroup.

Additionally or alternatively, each R¹ can be a C₂-C₇ alkynylene group,a C₁-C₆ alkynylene group, a C₂-C₅ alkynylene group, a C₂-C₄ a alkynylenegroup, a C₂-C₃ alkynylene group, or —C≡C—.

Additionally or alternatively, each Z²¹ can be a C₁-C₂ alkoxy group; Z²²and Z²³ each independently can be a C₁-C₂ alkoxy group or a C₁-C₂ alkylgroup; and R¹ can be a C₂-C₄ alkynylene group.

Additionally or alternatively, each Z²¹ can be a C₁-C₂ alkoxy group; Z²²and Z²³ each independently can be a C₁-C₂ alkoxy group or a C₁-C₂ alkylgroup; and each R¹ can be a C₂-C₄ alkylene group, a C₂-C₄ alkenylenegroup or a C₂-C₄ alkynylene group.

Additionally or alternatively, each 1Z¹ can be a nitrogen-containingC₂-C₁₀ alkylene group, a nitrogen-containing C₃-C₁₀ alkylene group, anitrogen-containing C₄-C₁₀ alkylene group, a nitrogen-containing C₄-C₉alkylene group, a nitrogen-containing C₄-C₈ alkylene group, or nitrogencontaining C₃-C₈ alkylene group. The aforementioned nitrogen-containingalkylene groups may have one or more nitrogen atoms (e.g., 2, 3, etc.).Examples of nitrogen-containing alkylene groups include, but are notlimited to,

Additionally or alternatively, each Z²¹ can be a C₁-C₂ alkoxy group; Z²²and Z²³ each independently can be a C₁-C₂ alkoxy group or a C₁-C₂ alkylgroup; and each 1Z¹ can be a nitrogen-containing C₄-C₁₀ alkylene group.

Additionally or alternatively, each Z²¹ can be a C₁-C₂ alkoxy group; Z²²and Z²³ each independently can be a C₁-C₂ alkoxy group or a C₁-C₂ alkylgroup; and each 1Z¹ can be a C₂-C₄ alkylene group, a C₂-C₄ alkenylenegroup, a C₂-C₄ alkynylene group or a nitrogen-containing C₄-C₁₀ alkylenegroup.

Additionally or alternatively, each 1Z¹ can be an optionally substitutedC₆-C₂₀ aralkyl, an optionally substituted C₆-C₁₄ aralkyl, or anoptionally substituted C₆-C₁₀ aralkyl. Examples of C₆-C₂₀ aralkylsinclude, but are not limited to, phenylmethyl, phenylethyl, andnaphthylmethyl. The aralkyl may be optionally substituted with a C₁-C₆alkyl group, particularly a C₁-C₄ alkyl group.

Additionally or alternatively, each Z²¹ can be a C₁-C₂ alkoxy group; Z²²and Z²³ each independently can be a C₁-C₂ alkoxy group or a C₁-C₂ alkylgroup; and each 1Z¹ can be an optionally substituted C₆-C₁₀ aralkyl.

Additionally or alternatively, each Z²¹ can be a C₁-C₂ alkoxy group; Z²²and Z²³ each independently can be a C₁-C₂ alkoxy group or a C₁-C₂ alkylgroup; and each R¹ can be a C₂-C₄ alkylene group, a C₂-C₄ alkenylenegroup, a C₂-C₄ alkynylene group, or an optionally substituted C₆-C₁₀aralkyl.

Additionally or alternatively, R¹ can be an optionally substitutedC₄-C₂₀ heterocycloalkyl group, an optionally substituted C₄-C₁₆heterocycloalkyl group, an optionally substituted C₄-C₁₂heterocycloalkyl group, or an optionally substituted C₄-C₁₀heterocycloalkyl group. Examples of C₄-C₂₀ heterocycloalkyl groupsinclude, but are not limited to, thienylmethyl, furylethyl,pyrrolylmethyl, piperazinylethyl, pyridylmethyl, benzoxazolylethyl,quinolinylpropyl, and imidazolylpropyl. The heterocycloalkyl may beoptionally substituted with a C₁-C₆ alkyl group, particularly a C₁-C₄alkyl group.

Additionally or alternatively, each Z²¹ can be a C₁-C₂ alkoxy group; Z²²and Z²³ each independently can be a C₁-C₂ alkoxy group or a C₁-C₂ alkylgroup; and R¹ can be an optionally substituted C₄-C₁₂ heterocycloalkylgroup.

Additionally or alternatively, each Z²¹ can be a C₁-C₂ alkoxy group; Z²²and Z²³ each independently can be a C₁-C₂ alkoxy group or a C₁-C₂ alkylgroup; and each R¹ can be a C₂-C₄ alkylene group, a C₂-C₄ alkenylenegroup, a C₂-C₄ alkynylene group, an optionally substituted C₆-C₁₀aralkyl, or an optionally substituted C₄-C₁₂ heterocycloalkyl group.

In a particular embodiment, Z²¹ and Z²² can be ethoxy, Z²³ can be methyland R¹ can be —CH₂CH₂—, such that compound corresponding to Formula (X)can be 1,2-bis(methyldiethoxysilyl)ethane(CH₃(EtO)₂Si—CH₂CH₂—Si(EtO)₂CH₃).

In another particular embodiment, a compound of Formula (VIII) can be1,1,3,3,5,5-hexaethoxy-1,3,5-trisilacyclohexane ([(EtO)₂SiCH₂]₃), and acompound of Formula (X) can be 1,2-bis(methyldiethoxysilyl)ethane (CH₃(EtO)₂Si—CH₂CH₂—Si(EtO)₂CH₃).

In another particular embodiment, Z²¹, Z²² and Z²³ can be ethoxy and R¹can be —CH₂—, such that compound corresponding to Formula (X) can bebis(triethoxysilyl)methane ((EtO)₃Si—CH₂—Si(EtO)₃).

In another particular embodiment, a compound of Formula (VIII) can be1,1,3,3,5,5-hexaethoxy-1,3,5-trisilacyclohexane ([(EtO)₂SiCH₂]₃) and acompound of Formula (X) can be bis(triethoxysilyl)methane((EtO)₃Si—CH₂—Si(EtO)₃).

In another particular embodiment, Z²¹, Z²² and Z²³ can be ethoxy and R¹can be —HC═CH—, such that compound corresponding to Formula (IX) can be1,2-bis(triethoxysilyl)ethylene ((EtO)₃Si—HC═CH—Si(EtO)₃).

In another particular embodiment, a compound of Formula (VIII) can be1,1,3,3,5,5-hexaethoxy-1,3,5-trisilacyclohexane ([(EtO)₂SiCH₂]₃)) and acompound of Formula (X) can be 1,2-bis(triethoxysilyl)ethylene((EtO)₃Si—HC═CH—Si(EtO)₃).

In another particular embodiment, a compound of Formula (X) can bebis(triethoxysilyl)methane ((EtO)₃Si—CH₂—Si(EtO)₃) and a compound ofFormula (IX) can be tetraethyl orthosilicate (TEOS) ((EtO)₄Si).

In a particular embodiment, Z²¹, Z²² and Z²³ can be methoxy and R¹ canbe

such that compound corresponding to Formula (X) can beN,N′-bis[(3-trimethoxysilyl)propyl]ethylenediamine.

In another particular embodiment, a compound of Formula (VIII) can be1,1,3,3,5,5-hexaethoxy-1,3,5-trisilacyclohexane ([(EtO)₂SiCH₂]₃) and acompound of Formula (X) can beN,N′-bis[(3-trimethoxysilyl)propyl]ethylenediamine.

In another particular embodiment, Z²¹ and Z²² can be ethoxy, Z²³ can bemethyl and R¹ can be

such that compound corresponding to Formula (X) can bebis[(methyldiethoxysilyl)propyl]amine.

In another particular embodiment, Formula (VIII) can be1,1,3,3,5,5-hexaethoxy-1,3,5-trisilacyclohexane ([(EtO)₂SiCH₂]₃) and acompound of Formula (X) can be bis[(methyldiethoxysilyl)propyl]amine.

In another particular embodiment, Z²¹ and Z²² can be methoxy, Z²³ can bemethyl and R¹ can be

such that compound corresponding to Formula (X) can bebis[(methyldimethoxysilyl)propyl]-N-methylamine.

In another particular embodiment, a compound of Formula (VIII) can be1,1,3,3,5,5-hexaethoxy-1,3,5-trisilacyclohexane ([(EtO)₂SiCH₂]₃) and acompound of Formula (X) can bebis[(methyldimethoxysilyl)propyl]-N-methylamine.

The molar ratio of compound of Formula (VIII) to compound of Formula (X)may vary within wide limits, such as from about 99:1 to about 1:99, fromabout 1:5 to about 5:1, from about 4:1 to about 1:4 or from about 3:2 toabout 2:3. For example, a molar ratio of compound of Formula (VIII) tocompound of Formula (X) can be from about 4:1 to 1:4 or from about 2.5:1to 1:2.5, about 2:1 to about 1:2, such as about 1.5:1 to about 1.5:1.

5. Sources of Trivalent Metal Oxide

In additional embodiments, the methods provided herein can compriseadding to the aqueous solution a source of a trivalent metal oxide.

Sources of trivalent metal oxides can include, but are not limited to,corresponding salts, alkoxides, oxides, and/or hydroxides of thetrivalent metal, e.g., aluminum sulphate, aluminum nitrate, colloidalalumina, aluminum trihydroxide, hydroxylated alumina, Al₂O₃, aluminumhalides (e.g., AlCl₃), NaAlO₂, boron nitride, B₂O₃ and/or H₃BO₃.

In various aspects, the source of trivalent metal oxide may be acompound of Formula M³(OZ²⁴)₃ (XI) to obtain an organosilica materialwhich is a copolymer comprising at least one independent unit Formula(I) as described herein, at least one independent unit of Formula (VI)as described herein and optionally at least one independent unit ofFormulas (II), (III), (IV), (V) and/or (VII) as described herein,wherein M³ can be a Group 13 metal and each Z²⁴ independently can be aC₁-C₆ alkyl group.

In one embodiment, M³ can be B, Al, Ga, In, Il, or Uut. In particular,M³ can be Al or B.

Additionally or alternatively, each Z²⁴ can be a C₁-C₆ alkyl group, aC₁-C₅ alkyl group, a C₁-C₄ alkyl group, a C₁-C₃ alkyl group, a C₁-C₂alkyl group or methyl. In particular, Z¹⁵ can be methyl, ethyl, propylor butyl.

Additionally or alternatively, M³ can be Al or B and each Z²⁴ can bemethyl, ethyl, propyl or butyl.

In a particular embodiment, M³ can be Al and each Z²⁴ can be methyl,such that compound corresponding to Formula (XI) can be aluminumtrimethoxide.

In a particular embodiment, M³ can be Al and each Z²⁴ can be ethyl, suchthat compound corresponding to Formula (XI) can be aluminum triethoxide.

In a particular embodiment, M³ can be Al and each Z²⁴ can be propyl,such that compound corresponding to Formula (XI) can be aluminumisopropoxide.

In a particular embodiment, M³ can be Al and each Z²⁴ can be butyl, suchthat compound corresponding to Formula (XI) can be aluminumtri-sec-butoxide.

In another particular embodiment, a compound of Formula (VIII) can be1,1,3,3,5,5-hexaethoxy-1,3,5-trisilacyclohexane, ([(EtO)₂SiCH₂]₃) and acompound of Formula (XI) can be selected from the group consisting ofaluminum trimethoxide, aluminum triethoxide, aluminum isopropoxide, andaluminum tri-sec-butoxide.

In another particular embodiment, a compound of Formula (VIII) can be1,1,3,3,5,5-hexaethoxy-1,3,5-trisilacyclohexane, ([(EtO)₂SiCH₂]₃) and acompound of Formula (XI) can be aluminum tri-sec-butoxide.

Additionally or alternatively, the source of trivalent metal oxide maybe a compound of Formula (Z²⁵O)₂M⁴-O—Si(OZ²⁶)₃ (XII) to obtain anorganosilica material which is a copolymer comprising at least oneindependent unit Formula (I) as described herein, at least oneindependent unit of Formula (VII) as described herein and optionally atleast one independent unit of Formulas (II), (III), (IV), (V) and/or(VI) as described herein, wherein M⁴ can be a Group 13 metal and Z²⁵ andZ²⁶ each independently can be a C₁-C₆ alkyl group.

In one embodiment, M⁴ can be B, Al, Ga, In, Il, or Uut. In particular,M⁴ can be Al or B.

Additionally or alternatively, Z²⁵ and Z²⁶ each independently can be aC₁-C₆ alkyl group, a C₁-C₅ alkyl group, a C₁-C₄ alkyl group, a C₁-C₃alkyl group, a C₁-C₂ alkyl group or methyl. In particular, Z²⁵ and Z²⁶each independently can be methyl, ethyl, propyl or butyl.

Additionally or alternatively, M⁴ can be Al or B and Z²⁵ and Z²⁶ eachindependently can be methyl, ethyl, propyl or butyl.

Additionally or alternatively, the source of a trivalent metal oxide maybe a source of a compound of Formula (XI) (e.g., AlCl₃), and/or a sourceof a compound of Formula (XII).

The molar ratio of compound of Formula (VIII) to trivalent metal oxidemay vary within wide limits, such as from about 99:1 to about 1:99, fromabout 30:1 to about 1:1, from about 25:1 to about 1:1, from about 20:1to about 3:1 or from about 20:1 to about 5:1.

6. Compounds of Formula (XIII)

In additional embodiments, the methods provided herein can furthercomprise adding to the aqueous solution a cyclic compound of Formula

to obtain an organosilica material which is a copolymer comprising atleast one independent unit of Formula (I) as described herein, at leastone independent unit of Formula (V) as described herein and optionallyat least one independent unit of Formulas (II), (III), (IV), (VI) and/or(VII) as described herein, wherein each R³ independently can be aX⁵OX⁶X⁷SiX⁸ group, wherein each X⁵ can be a C₁-C₄ alkyl group; X⁶ and X⁷each independently can be a C₁-C₄ alkyl group or a C₁-C₄ alkoxy group;and each X⁸ can be a C₁-C₈ alkylene group bonded to a nitrogen atom ofthe cyclic compound.

In various embodiments, each X⁵ can be a C₁-C₄ alkyl, a C₁-C₃ alkyl, aC₁-C₂ alkyl or methyl.

Additionally or alternatively, each X⁶ and X⁷ each independently can bea C₁-C₄ alkyl group, a C₁-C₃ alkyl group, a C₁-C₂ alkyl group or methyl.

Additionally or alternatively, each X⁶ and X⁷ each independently can bea C₁-C₄ alkoxy group, a C₁-C₃ alkoxy group, a C₁-C₂ alkoxy group ormethoxy.

Additionally or alternatively, each X⁶ and X⁷ each independently can bea C₁-C₂ alkyl group or a C₁-C₂ alkoxy group.

Additionally or alternatively, each X⁵ can be C₁-C₂ alkyl group; and X⁶and X⁷ each independently can be a C₁-C₂ alkyl group or a C₁-C₂ alkoxygroup.

Additionally or alternatively, each X⁸ can be a C₁-C₇ alkylene groupbonded to a nitrogen atom of the cyclic compound, a C₁-C₇ alkylene groupbonded to a nitrogen atom of the cyclic compound, a C₁-C₆ alkylene groupbonded to a nitrogen atom of the cyclic compound, a C₁-C₄ alkylene groupbonded to a nitrogen atom of the cyclic compound, a C₁-C₃ alkylene groupbonded to a nitrogen atom of the cyclic compound, a C₁-C₂ alkylene groupbonded to a nitrogen atom of the cyclic compound, or —CH₂— bonded to anitrogen atom of the cyclic compound.

Additionally or alternatively, each X⁵ can be a C₁-C₂ alkyl group; X⁶and X⁷ each independently can be a C₁-C₂ alkyl group or a C₁-C₂ alkoxygroup; and X⁸ can be a C₁-C₄ alkylene group bonded to a nitrogen atom ofthe cyclic compound.

In a particular embodiment, each X⁵ can be methyl; X⁶ and X⁷ eachindependently can be methoxy; and X⁸ can be —CH₂CH₂CH₂—, such that thecompound corresponding to Formula (XIII) can betris(3-trimethoxysilylpropyl)isocyanurate.

In another particular embodiment, a compound of Formula (VIII) can be1,1,3,3,5,5-hexaethoxy-1,3,5-trisilacyclohexane ([(EtO)₂SiCH₂]₃) and acompound of Formula (XIII) can betris(3-trimethoxysilylpropyl)isocyanurate.

In another particular embodiment, compound of Formula (IX) can betetraethyl orthosilicate (TEOS) ((EtO)₄Si) and a compound of Formula(XIII) can be tris(3-trimethoxysilylpropyl)isocyanurate.

In various aspects, only a compound of Formula (XIII) (e.g.,tris(3-trimethoxysilylpropyl)isocyanurate) can be added to the aqueousmixture and no other compounds of Formulas (VIII)-(XII).

In various aspects, only a compound of Formula (XIII) (e.g.,tris(3-trimethoxysilylpropyl)isocyanurate) and compound of Formula (IX)(e.g., tetraethyl orthosilicate (TEOS) ((EtO)₄Si)) can be added to theaqueous mixture and no other compounds of Formulas (VIII)-(XII).

7. Metal Chelate Sources

In additional embodiments, the methods provided herein can furthercomprise adding to the aqueous solution a source of metal chelatecompounds.

Examples of metal chelate compounds, when present, can include titaniumchelate compounds such as triethoxy.mono(acetylacetonato) titanium,tri-n-propoxy.mono(acetylacetonato)titanium,tri-i-propoxy.mono(acetylacetonato)titanium,tri-n-butoxy.mono(acetylacetonato)titanium,tri-sec-butoxy.mono(acetylacetonato)titanium,tri-t-butoxy.mono(acetylacetonato)titanium,diethoxy.bis(acetylacetonato)titanium,di-n-propoxy.bis(acetylacetonato)titanium,di-i-propoxy.bis(acetylacetonato)titanium,di-n-butoxy.bis(acetylacetonato)titanium,di-sec-butoxy.bis(acetylacetonato)titanium,di-t-butoxy.bis(acetylacetonato)titanium,monoethoxy.tris(acetylacetonato)titanium,mono-n-propoxy.tris(acetylacetonato) titanium,mono-i-propoxy.tris(acetylacetonato)titanium,mono-n-butoxy.tris(acetylacetonato)titanium,mono-sec-butoxy.tris(acetylacetonato)titanium,mono-t-butoxy-tris(acetylacetonato)titanium,tetrakis(acetylacetonato)titanium,triethoxy.mono(ethylacetoacetaato)titanium,tri-n-propoxy.mono(ethylacetoacetato)titanium,tri-i-propoxy.mono(ethylacetoacetato)titanium,tri-n-butoxy.mono(ethylacetoacetato)titanium,tri-sec-butoxy.mono(ethylacetoacetato)titanium,tri-t-butoxy-mono(ethylacetoacetato)titanium,diethoxy.bis(ethylacetoacetato)titanium,di-n-propoxy.bis(ethylacetoacetato)titanium,di-i-propoxy.bis(ethylacetoacetato)titanium,di-n-butoxy.bis(ethylacetoacetato)titanium,di-sec-butoxy.bis(ethylacetoacetato)titanium,di-t-butoxy.bis(ethylacetoacetato)titanium,monoethoxy.tris(ethylacetoacetato)titanium,mono-n-propoxy.tris(ethylacetoaetato)titanium,mono-i-propoxy.tris(ethylacetoacetato)titanium,mono-n-butoxy.tris(ethylacetoacetato)titanium,mono-sec-butoxy.tris(ethylacetoacetato)titanium,mono-t-butoxy.tris(ethylacetoacetato)titanium,tetrakis(ethylacetoacetato)titanium,mono(acetylacetonato)tris(ethylacetoacetato)titanium,bis(acetylacetonato)bis(ethylacetoacetato)titanium, andtris(acetylacetonato)mono(ethylacetoacetato)titanium; zirconium chelatecompounds such as triethoxy.mono(acetylacetonato)zirconium,tri-n-propoxy.mono(acetylacetonato)zirconium,tri-i-propoxy.mono(acetylacetonato)zirconium,tri-n-butoxy.mono(acetylacetonato)zirconium,tri-sec-butoxy.mono(acetylacetonato)zirconium,tri-t-butoxy.mono(acetylacetonato)zirconium,diethoxy.bis(acetylacetonato)zirconium,di-n-propoxy.bis(acetylacetonato)zirconium,di-i-propoxy.bis(acetylacetonato)zirconium,di-n-butoxy.bis(acetylacetonato)zirconium,di-sec-butoxy.bis(acetylacetonato)zirconium,di-t-butoxy.bis(acetylacetonato)zirconium,monoethoxy.tris(acetylacetonato)zirconium,mono-n-propoxy.tris(acetylacetonato)zirconium,mono-i-propoxy.tris(acetylacetonato)zirconium,mono-n-butoxy.tris(acetylacetonato)zirconium,mono-sec-butoxy.tris(acetylacetonato)zirconium,mono-t-butoxy.tris(acetylacetonato)zirconium,tetrakis(acetylacetonato)zirconium,triethoxy.mono(ethylacetoacetato)zirconium,tri-n-propoxy.mono(ethylacetoacetato)zirconium,tri-i-propoxy.mono(ethylacetoacetato)zirconium,tri-n-butoxy.mono(ethylacetoacetato)zirconium,tri-sec-butoxy.mono(ethylacetoacetato)zirconium,tri-t-butoxy.mono(ethylacetoacetato)zirconium,diethoxy.bis(ethylacetoacetato)zirconium,di-n-propoxy.bis(ethylacetoacetato)zirconium,di-i-propoxy.bis(ethylacetoacetato)zirconium,di-n-butoxy.bis(ethylacetoacetato)zirconium,di-sec-butoxy.bis(ethylacetoacetato)zirconium,di-t-butoxy.bis(ethylacetoacetato)zirconium,monoethoxy.tris(ethylacetoacetato)zirconium,mono-n-propoxy.tris(ethylacetoacetato)zirconium,mono-i-propoxy.tris(ethylacetoacetato)zirconium,mono-n-butoxy.tris(ethylacetoacetato)zirconium,mono-sec-butoxy.tris(ethylacetoacetato)zirconium,mono-t-butoxy.tris(ethylacetoacetato)zirconium,tetrakis(ethylacetoacetato)zirconium,mono(acetylacetonato)tris(ethylacetoacetato) zirconium,bis(acetylacetonato)bis(ethylacetoacetato)zirconium, andtris(acetylacetonato)mono(ethylacetoacetato)zirconium; and aluminumchelate compounds such as tris(acetylacetonato)aluminum andtris(ethylacetoacetato)aluminum. Of these, the chelate compounds oftitanium or aluminum can be of note, of which the chelate compounds oftitanium can be particularly of note. These metal chelate compounds maybe used either singly or in combination

8. Molar Ratio

In the methods described herein, a molar ratio of Formula (VIII):Formula (VIII), Formula (VIII): Formula (IX), Formula (VIII): Formula(X), Formula (X): Formula (IX), Formula (VIII): Formula (XI), Formula(VIII): Formula (XII), Formula (VIII): Formula (XIII) and Formula(XIII): Formula (IX) of about 99:1 to about 1:99, about 75:1 to about1:99, about 50:1 to about 1:99, about 25:1 to about 1:99, about 15:1 toabout 1:99, about 50:1 to about 1:50, about 25:1 to about 1:25 or about15:1 to about 1:15 may be used. For example, molar ratios of about 3:2,about 4:1, about 4:3, about 5:1, about 2:3, about 1:1, 1:1.5 about 5:2and about 15:1 may be used. For example, a molar ratio of Formula(VIII): Formula (VIII) can be about 3:2. A molar ratio of Formula(VIII): Formula (IX) can be about 2:3, about 4:3, about 4:1 or about3:2. A molar ratio of Formula (VIII): Formula (X) can be about 2:3, andabout 4:1. A molar ratio of Formula (X): Formula (IX) can be about 5:2,about 1:1, about 1:2 or about 2:3. A molar ratio of Formula (VIII):Formula (XI) and Formula (VIII): Formula (XII) can be about 15:1 orabout 5:1. A molar ratio of Formula (XIII): Formula (IX) can be about1:1.5. A molar ratio of Formula (XIII): Formula (VIII) can be about 2:3.

For the sake of the following discussion, the compounds of Formula(VIII), (IX) and (X) shall be referred to collectively as startingsiloxane. Depending on the choice of starting materials, the solutionmay have a variety of compositions. For example, if base is used, thesolution may have molar ratios of starting siloxane to OH⁻ of from about1:5 to about 1:20, such as from about 1:5 to about 1:15 or from about1:5 to 1:10, or from about 1:6 to 1:20. If acid is used, the solutionmay have molar ratios of starting siloxane:H⁺ of from about 50:1 toabout 5:1, such as from about 45:1 to about 10:1. In both cases whenacid or base is used, the molar ratios of starting siloxane to H₂O mayvary from about 1:50 to about 1:1000, such as from about 1:100 to about1:500.

9. Aging the Solution

The solution formed in the methods described herein can be aged for atleast about 4 hours, at least about 6 hours, at least about 12 hours, atleast about 18 hours, at least about 24 hours (1 day), at least about 30hours, at least about 36 hours, at least about 42 hours, at least about48 hours (2 days), at least about 54 hours, at least about 60 hours, atleast about 66 hours, at least about 72 hours (3 days), at least about96 hours (4 days), at least about 120 hours (5 days) or at least about144 hours (6 days).

Additionally or alternatively, the solution formed in the methodsdescribed herein can be aged for about 4 hours to about 144 hours (6days), about 4 hours to about 120 hours (5 days), about 4 hours to about96 hours (4 days), about 4 hours to about 72 hours (3 days), about 4hours to about 66 hours, about 4 hours to about 60 hours, about 4 hoursto about 54 hours, about 4 hours to about 48 hours (2 days), about 4hours to about 42 hours, about 4 hours to about 36 hours, about 4 hoursto about 30 hours, about 4 hours to about 24 hours (1 day), about 4hours to about 18 hours, about 4 hours to about 12 hours, about 4 hoursto about 6 hours, about 6 hours to about 144 hours (6 days), about 6hours to about 120 hours (5 days), about 6 hours to about 96 hours (4days), about 6 hours to about 72 hours (3 days), about 6 hours to about66 hours, about 6 hours to about 60 hours, about 6 hours to about 54hours, about 6 hours to about 48 hours (2 days), about 6 hours to about42 hours, about 6 hours to about 36 hours, about 6 hours to about 30hours, about 6 hours to about 24 hours (1 day), about 6 hours to about18 hours, about 6 hours to about 12 hours, about 12 hours to about 144hours (6 days), about 12 hours to about 120 hours (5 days), about 12hours to about 96 hours (4 days), about 12 hours to about 72 hours (3days), about 12 hours to about 66 hours, about 12 hours to about 60hours, about 12 hours to about 54 hours, about 12 hours to about 48hours (2 days), about 12 hours to about 42 hours, about 12 hours toabout 36 hours, about 12 hours to about 30 hours, about 12 hours toabout 24 hours (1 day), about 12 hours to about 18 hours, about 18 hoursto about 144 hours (6 days), about 18 hours to about 120 hours (5 days),about 18 hours to about 96 hours (4 days), about 18 hours to about 72hours (3 days), about 18 hours to about 66 hours, about 18 hours toabout 60 hours, about 18 hours to about 54 hours, about 18 hours toabout 48 hours (2 days), about 18 hours to about 42 hours, about 18hours to about 36 hours, about 18 hours to about 30 hours, about 18hours to about 24 hours (1 day), about 24 hours (1 day) to about 144hours (6 days), about 24 (1 day) hours (1 day) to about 120 hours (5days), about 24 hours (1 day) to about 96 hours (4 days), about 24 hours(1 day) to about 72 hours (3 days), about 24 hours (1 day) to about 66hours, about 24 hours (1 day) to about 60 hours, about 24 hours (1 day)to about 54 hours, about 24 hours (1 day) to about 48 hours (2 days),about 24 hours (1 day) to about 42 hours, about 24 hours (1 day) toabout 36 hours, about 24 hours (1 day) to about 30 hours, about 30 hoursto about 144 hours (6 days), about 30 hours to about 120 hours (5 days),about 30 hours to about 96 hours (4 days), about 30 hours to about 72hours (3 days), about 30 hours to about 66 hours, about 30 hours toabout 60 hours, about 30 hours to about 54 hours, about 30 hours toabout 48 hours (2 days), about 30 hours to about 42 hours, about 30hours to about 36 hours, about 36 hours to about 144 hours (6 days),about 36 hours to about 120 hours (5 days), about 36 hours to about 96hours (4 days), about 36 hours to about 72 hours (3 days), about 36hours to about 66 hours, about 36 hours to about 60 hours, about 36hours to about 54 hours, about 36 hours to about 48 hours (2 days),about 36 hours to about 42 hours, about 42 hours to about 144 hours (6days), about 42 hours to about 120 hours (5 days), about 42 hours toabout 96 hours (4 days), about 42 hours to about 72 hours (3 days),about 42 hours to about 66 hours, about 42 hours to about 60 hours,about 42 hours to about 54 hours, about 42 hours to about 48 hours (2days), about 48 hours (2 days) to about 144 hours (6 days), about 48hours (2 days) to about 120 hours (5 days), about 48 hours (2 days) toabout 96 hours (4 days), about 48 hours (2 days) to about 72 hours (3days), about 48 hours (2 days) to about 66 hours, about 48 hours (2days) to about 60 hours, about 48 hours (2 days) to about 54 hours,about 54 hours to about 144 hours (6 days), about 54 hours to about 120hours (5 days), about 54 hours to about 96 hours (4 days), about 54hours to about 72 hours (3 days), about 54 hours to about 66 hours,about 54 hours to about 60 hours, about 60 hours to about 144 hours (6days), about 60 hours to about 120 hours (5 days), about 60 hours toabout 96 hours (4 days), about 60 hours to about 72 hours (3 days),about 60 hours to about 66 hours, about 66 hours to about 144 hours (6days), about 66 hours to about 120 hours (5 days), about 66 hours toabout 96 hours (4 days), about 66 hours to about 72 hours (3 days),about 72 hours (3 days) to about 144 hours (6 days), about 72 hours (3days) to about 120 hours (5 days), about 72 hours (3 days) to about 96hours (4 days), about 96 hours (4 days) to about 144 hours (6 days),about 96 hours (4 days) to about 120 hours (5 days), or about 120 hours(5 days) to about 144 hours (6 days).

Additionally or alternatively, the solution formed in the method can beaged at temperature of at least about 10° C., at least about 20° C., atleast about 30° C., at least about 40° C., at least about 50° C., atleast about 60° C., at least about 70° C., at least about 80° C., atleast about 90° C., at least about 100° C., at least about 110° C., atleast about 120° C. at least about 130° C., at least about 140° C., atleast about 150° C., at least about 175° C., at least about 200° C., atleast about 250° C., or about 300° C.

Additionally or alternatively, the solution formed in the method can beaged at temperature of about 10° C. to about 300° C., about 10° C. toabout 250° C., about 10° C. to about 200° C., about 10° C. to about 175°C., about 10° C. to about 150° C., about 10° C. to about 140° C., about10° C. to about 130° C., about 10° C. to about 120° C., about 10° C. toabout 110° C., about 10° C. to about 100° C., about 10° C. to about 90°C., about 10° C. to about 80° C., about 10° C. to about 70° C., about10° C. to about 60° C., about 10° C. to about 50° C., about 20° C. toabout 300° C., about 20° C. to about 250° C., about 20° C. to about 200°C., about 20° C. to about 175° C., about 20° C. to about 150° C., about20° C. to about 140° C., about 20° C. to about 130° C., about 20° C. toabout 120° C., about 20° C. to about 110° C., about 20° C. to about 100°C., about 20° C. to about 90° C., about 20° C. to about 80° C., about20° C. to about 70° C., about 20° C. to about 60° C., about 20° C. toabout 50° C., about 30° C. to about 300° C., about 30° C. to about 250°C., about 30° C. to about 200° C., about 30° C. to about 175° C., about30° C. to about 150° C., about 30° C. to about 140° C., about 30° C. toabout 130° C., about 30° C. to about 120° C., about 30° C. to about 110°C., about 30° C. to about 100° C., about 30° C. to about 90° C., about30° C. to about 80° C., about 30° C. to about 70° C., about 30° C. toabout 60° C., about 30° C. to about 50° C., about 50° C. to about 300°C., about 50° C. to about 250° C., about 50° C. to about 200° C., about50° C. to about 175° C., about 50° C. to about 150° C., about 50° C. toabout 140° C., about 50° C. to about 130° C., about 50° C. to about 120°C., about 50° C. to about 110° C., about 50° C. to about 100° C., about50° C. to about 90° C., about 50° C. to about 80° C., about 50° C. toabout 70° C., about 50° C. to about 60° C., about 70° C. to about 300°C., about 70° C. to about 250° C., about 70° C. to about 200° C., about70° C. to about 175° C., about 70° C. to about 150° C., about 70° C. toabout 140° C., about 70° C. to about 130° C., about 70° C. to about 120°C., about 70° C. to about 110° C., about 70° C. to about 100° C., about70° C. to about 90° C., about 70° C. to about 80° C., about 80° C. toabout 300° C., about 80° C. to about 250° C., about 80° C. to about 200°C., about 80° C. to about 175° C., about 80° C. to about 150° C., about80° C. to about 140° C., about 80° C. to about 130° C., about 80° C. toabout 120° C., about 80° C. to about 110° C., about 80° C. to about 100°C., about 80° C. to about 90° C., about 90° C. to about 300° C., about90° C. to about 250° C., about 90° C. to about 200° C., about 90° C. toabout 175° C., about 90° C. to about 150° C., about 90° C. to about 140°C., about 90° C. to about 130° C., about 90° C. to about 120° C., about90° C. to about 110° C., about 90° C. to about 100° C., about 100° C. toabout 300° C., about 100° C. to about 250° C., about 100° C. to about200° C., about 100° C. to about 175° C., about 100° C. to about 150° C.,about 100° C. to about 140° C., about 100° C. to about 130° C., about100° C. to about 120° C., about 100° C. to about 110° C., about 110° C.to about 300° C., about 110° C. to about 250° C., about 110° C. to about200° C., about 110° C. to about 175° C., about 110° C. to about 150° C.,about 110° C. to about 140° C., about 110° C. to about 130° C., about110° C. to about 120° C., about 120° C. to about 300° C., about 120° C.to about 250° C., about 120° C. to about 200° C., about 120° C. to about175° C., about 120° C. to about 150° C., about 120° C. to about 140° C.,about 120° C. to about 130° C., about 130° C. to about 300° C., about130° C. to about 250° C., about 130° C. to about 200° C., about 130° C.to about 175° C., about 130° C. to about 150° C., or about 130° C. toabout 140° C.

10. Drying the Pre-Product

The methods described herein comprise drying the pre-product (e.g., agel) to produce an organosilica material support.

In some embodiments, the pre-product (e.g., a gel) formed in the methodcan be dried at a temperature of greater than or equal to about 50° C.,greater than or equal to about 70° C., greater than or equal to about80° C., greater than or equal to about 100° C., greater than or equal toabout 110° C., greater than or equal to about 120° C., greater than orequal to about 150° C., greater than or equal to about 200° C., greaterthan or equal to about 250° C., greater than or equal to about 300° C.,greater than or equal to about 350° C., greater than or equal to about400° C., greater than or equal to about 450° C., greater than or equalto about 500° C., greater than or equal to about 550° C., or greaterthan or equal to about 600° C.

Additionally or alternatively, the pre-product (e.g., a gel) formed inthe method can be dried at temperature of about 50° C. to about 600° C.,about 50° C. to about 550° C., about 50° C. to about 500° C., about 50°C. to about 450° C., about 50° C. to about 400° C., about 50° C. toabout 350° C., about 50° C. to about 300° C., about 50° C. to about 250°C., about 50° C. to about 200° C., about 50° C. to about 150° C., about50° C. to about 120° C., about 50° C. to about 110° C., about 50° C. toabout 100° C., about 50° C. to about 80° C., about 50° C. to about 70°C., about 70° C. to about 600° C., about 70° C. to about 550° C., about70° C. to about 500° C., about 70° C. to about 450° C., about 70° C. toabout 400° C., about 70° C. to about 350° C., about 70° C. to about 300°C., about 70° C. to about 250° C., about 70° C. to about 200° C., about70° C. to about 150° C., about 70° C. to about 120° C., about 70° C. toabout 110° C., about 70° C. to about 100° C., about 70° C. to about 80°C., about 80° C. to about 600° C., about 70° C. to about 550° C., about80° C. to about 500° C., about 80° C. to about 450° C., about 80° C. toabout 400° C., about 80° C. to about 350° C., about 80° C. to about 300°C., about 80° C. to about 250° C., about 80° C. to about 200° C., about80° C. to about 150° C., about 80° C. to about 120° C., about 80° C. toabout 110° C., or about 80° C. to about 100° C.

In a particular embodiment, the pre-product (e.g., a gel) formed in themethod can be dried at temperature from about 70° C. to about 200° C.

Additionally or alternatively, the pre-product (e.g., a gel) formed inthe method can be dried in a N₂ and/or air atmosphere.

11. Optional Further Steps

In some embodiments, the method can further comprise calcining theorganosilica material to obtain a silica material. The calcining can beperformed in air or an inert gas, such as nitrogen or air enriched innitrogen. Calcining can take place at a temperature of at least about300° C., at least about 350° C., at least about 400° C., at least about450° C., at least about 500° C., at least about 550° C., at least about600° C., or at least about 650° C., for example at least about 400° C.Additionally or alternatively, calcining can be performed at atemperature of about 300° C. to about 650° C., about 300° C. to about600° C., about 300° C. to about 550° C., about 300° C. to about 400° C.,about 300° C. to about 450° C., about 300° C. to about 400° C., about300° C. to about 350° C., about 350° C. to about 650° C., about 350° C.to about 600° C., about 350° C. to about 550° C., about 350° C. to about400° C., about 350° C. to about 450° C., about 350° C. to about 400° C.,about 400° C. to about 650° C., about 400° C. to about 600° C., about400° C. to about 550° C., about 400° C. to about 500° C., about 400° C.to about 450° C., about 450° C. to about 650° C., about 450° C. to about600° C., about 450° C. to about 550° C., about 450° C. to about 500° C.,about 500° C. to about 650° C., about 500° C. to about 600° C., about500° C. to about 550° C., about 550° C. to about 650° C., about 550° C.to about 600° C. or about 600° C. to about 650° C.

IV. ADSORBENT MATERIAL PRODUCT-BY-PROCESS

Adsorbent materials can be made from the methods described herein. Inanother particular embodiment, adsorbent materials can be made from anaqueous mixture as described herein that contains essentially nostructure directing agent or porogen as described herein to form anorganosilica material support as described herein and a Group 8 metalion as described herein, wherein the organosilica material may be:

-   -   (i) a homopolymer comprising units of Formula (I) as described        herein;    -   (ii) a homopolymer comprising units of Formula (V) as described        herein; or    -   (iii) a copolymer comprising independent units of Formula (I) as        described herein and at least one other monomer comprising units        of Formulas (II) (III), (IV), (V), (VI) and/or (VII) as        described herein.

V. HETEROATOM SPECIES REMOVAL

In various embodiments, methods for separating a heteroatom species froma hydrocarbon feedstream are provided herein. The method can comprisecontacting a hydrocarbon feedstream containing at least one heteroatomspecies with the adsorbent material as described herein. Additionally oralternatively, the adsorbent material may be packed into a column or abed, and the hydrocarbon feedstream may travel through the column or thebed.

Suitable hydrocarbon feedstreams include any conventional hydrocarbonfeedstreams where heteroatom species removal is desirable. Suchfeedstreams can include hydrocarbon fluids, whole crude, diesel,kerosene, virgin diesel, light gas oil (LGO), lubricating oilfeedstreams, heavy coker gasoil (HKGO), de-asphalted oil (DAO), fluidcatalytic cracking (FCC) main column bottom (MCB), and steam crackertar. Such feedstreams can also include other distillate feedstreams,including wax-containing feedstreams such as feeds derived from crudeoils, shale oils and tar sands. Synthetic feeds such as those derivedfrom the Fischer-Tropsch process can also be aromatically saturatedusing the hydrogenation catalyst described herein. Typicalwax-containing feedstocks for the preparation of lubricating base oilshave initial boiling points of about 315° C. or higher, and includefeeds such as reduced crudes, hydrocrackates, raffinates, hydrotreatedoils, atmospheric gas oils, vacuum gas oils, coker gas oils, atmosphericand vacuum residues, deasphalted oils, slack waxes and Fischer-Tropschwax. Such feeds may be derived from distillation towers (atmospheric andvacuum), hydrocrackers, hydrotreaters and solvent extraction units, andmay have wax contents of up to 50% or more. Preferred lubricating oilboiling range feedstreams include feedstreams which boil in the range of570-760° F. Diesel boiling range feedstreams include feedstreams whichboil in the range of 480-660° F. Kerosene boiling range feedstreamsinclude feedstreams which boil in the range of 350-617° F.

Hydrocarbon feedstreams suitable for use herein contain heteroatomspecies, such as but not limited to nitrogen-containing species,sulfur-containing species, oxygen-containing species and combinationsthereof. In particular, the heteroatom species comprisesnitrogen-containing species and/or sulfur-containing species. Examplesof nitrogen-containing species include, but are not limited tocarbazoles, imidazoles, pyrroles, quinones, quinilines and combinationsthereof. Examples of sulfur-containing species include, but are notlimited to mercaptans, thiols, disulfides, thiophenes, benzothiophenes,dibenzothiophenes and combinations thereof. Examples ofoxygen-containing species include, but are not limited to furans,indoles, carbazoles, benzcarbazoles, pyridines, quinolines,phenanthridine s, hydroxypyridines, hydroxyquinolines, dibenzofuranes,naphthobenzofuranes, phenols, aliphatic ketones, carboxylic acids, andsulfoxides. Lesser amounts of azaindoles, azacarbazoles, phenyl ketones,2-hydroxybiphenyls, benzofuranes, aliphatic esters and ethers, aliphaticdi-carbonyl compounds (diketones, diesters, etc.) and combinationsthereof. The feedstreams may contain up to 1 wt. % of nitrogen, based onthe feedstream, up to 5 wt. % of sulfur, and up to 5 wt. % oxygen.

In various embodiments, the sulfur content or the nitrogen content ofthe feedstreams can be below about 2500 wppm, below about 2250 wppm,below about 2000 wppm, below about 1750 wppm, below about 1500 wppm,below about 1250 wppm, below about 1000 wppm, below about 900 wppm,below about 800 wppm, below about 700 wppm, below about 600 wppm, belowabout 500 wppm, below about 400 wppm, below about 300 wppm, below about200 wppm, below about 100 wppm, below about 50 wppm, or below about 20wppm. Feeds having a high wax content typically have high viscosityindexes of up to 200 or more. Sulfur and nitrogen contents may bemeasured by standard ASTM methods D5453 and D4629, respectively.

In various aspects, heteroatom species (e.g., nitrogen-containingspecies, sulfur-containing species) can be separated from thehydrocarbon feedstream in amount of at least about 5%, at least about10%, at least about 15%, at least about 20%, at least about 25%, atleast about 30%, at least about 35%, at least about 40%, at least about45%, at least about 50%, at least about 55%, at least about 60%, atleast about 65%, at least about 70%, at least about 75%, at least about80%, at least about 85%, at least about 90%, at least about 95%, orabout 99%. In particular, at least about 20% of the nitrogen-containingspecies and/or at least about 10% of the sulfur-containing species canbe separated from the hydrocarbon feedstream.

Additionally or alternatively, the heteroatom species ((e.g.,nitrogen-containing species, sulfur-containing species) can be separatedfrom the hydrocarbon feedstream to produce a product feedstreamcomprising less heteroatom species than the hydrocarbon feedstream. Theheteroatom species ((e.g., nitrogen-containing species,sulfur-containing species) can be separated from the hydrocarbonfeedstream in amount about 5% to about 99%, about 5% to about 95%, about5% to about 90%, about 5% to about 85%, about 5% to about 80%, about 5%to about 75%, about 5% to about 70%, about 5% to about 65%, about 5% toabout 60%, about 5% to about 55%, about 5% to about 50%, about 5% toabout 45%, about 5% to about 40%, about 5% to about 35%, about 5% toabout 30%, about 5% to about 25%, about 5% to about 20%, about 5% toabout 15%, about 5% to about 10%, about 10% to about 99%, about 10% toabout 95%, about 10% to about 90%, about 10% to about 85%, about 10% toabout 80%, about 10% to about 75%, about 10% to about 70%, about 10% toabout 65%, about 10% to about 60%, about 10% to about 55%, about 10% toabout 50%, about 10% to about 45%, about 10% to about 40%, about 10% toabout 35%, about 10% to about 30%, about 10% to about 25%, about 10% toabout 20%, about 10% to about 15%, about 20% to about 99%, about 20% toabout 95%, about 20% to about 90%, about 20% to about 85%, about 20% toabout 80%, about 20% to about 75%, about 20% to about 70%, about 20% toabout 65%, about 20% to about 60%, about 20% to about 55%, about 20% toabout 50%, about 20% to about 45%, about 20% to about 40%, about 20% toabout 35%, about 20% to about 30%, about 20% to about 25%, about 40% toabout 99%, about 40% to about 95%, about 40% to about 90%, about 40% toabout 85%, about 40% to about 80%, about 40% to about 75%, about 40% toabout 70%, about 40% to about 65%, about 40% to about 60%, about 40% toabout 55%, about 40% to about 50% or about 40% to about 45%. Inparticular, the heteroatom species (e.g., nitrogen-containing species,sulfur-containing species) can be separated from the hydrocarbonfeedstream in amount about 5% to about 99%, about 5% to about 95%, about10% to about 95%, about 10% to about 90%, about 20% to about 90% orabout 40% to about 95%.

Advantageously, separation of the heteroatom species can occur at roomtemperature and atmospheric pressure. Effective separation conditionscan include temperatures of about 15° C. to about 30° C. and pressuresof from about 90 kPa to about 200 kPa. Additionally or alternatively,separation can be performed at higher temperatures of about 30° C. toabout 200° C.

As stated above, in some instances, the hydrocarbon feedstream may behydrotreated, e.g., to reduce the sulfur contaminants to below about 500wppm, particularly below about 300 wppm, particularly below about 200wppm or particularly below about 100 wppm. Hydrotreating may occur afterthe hydrocarbon feed is contacted with the adsorbent material asdescribed herein. In such an embodiment, the process may comprise atleast a separation stage and a reaction stage, the separation statecontaining the adsorbent material described herein and operated undereffective separation conditions, and the reaction stage containing ahydrotreating catalyst operated under effective hydrotreatingconditions. Therefore, in such an embodiment, the hydrocarbon feedstreamcan be first contacted with the adsorbent material as described hereinunder effective separation condition in order to reduce the heteroatomspecies (e.g., nitrogen-containing species, sulfur-containing species).Then the hydrocarbon feedstream can be contacted with a hydrotreatingcatalyst in the presence of a hydrogen-containing treat gas in areaction stage operated under effective hydrotreating conditions inorder to further reduce the sulfur content of the feedstream.Hydrogen-containing treat gasses can be comprised of substantially purehydrogen or can be mixtures of other components typically found inrefinery hydrogen streams. It is preferred that the hydrogen-containingtreat gas stream contains little, more preferably no, hydrogen sulfide.The hydrogen-containing treat gas purity should be at least about 50% byvolume hydrogen, preferably at least about 75% by volume hydrogen, andmore preferably at least about 90% by volume hydrogen for best results.It is most preferred that the hydrogen-containing stream besubstantially pure hydrogen.

Thus, the term “hydrotreating” as used herein refers to processeswherein a hydrogen-containing treat gas is used in the presence of asuitable catalyst that is active for the removal of heteroatoms, such assulfur, and nitrogen. Suitable hydrotreating catalysts for use in thepresent invention are any conventional hydrotreating catalyst andincludes those which are comprised of at least one Group 8 metal,preferably Fe, Co and Ni, more preferably Co and/or Ni, and mostpreferably Co; and at least one Group 6 metal, preferably Mo and W, morepreferably Mo, on a high surface area support material, preferablyalumina. Additionally or alternatively, more than one type ofhydrotreating catalyst can be used in the same reaction vessel. TheGroup 8 metal may typically be present in an amount ranging from about 2to 20 wt. %, preferably from about 4 to 12 wt. %. The Group 6 metal cantypically be present in an amount ranging from about 5 to 50 wt. %,preferably from about 10 to 40 wt. %, and more preferably from about 20to 30 wt. %. All metals weight percents are on support.

Effective hydrotreating conditions may be considered to be thoseconditions that can effectively reduce the sulfur content of thefeedstream (e.g., lube oil boiling range) to within the above-describedranges. Typical effective hydrotreating conditions can includetemperatures ranging from about 150° C. to about 425° C., preferablyabout 200° C. to about 370° C., more preferably about 230° C. to about350° C. Typical weight hourly space velocities (“WHSV”) may range fromabout 0.1 to about 20 hr⁻¹, preferably from about 0.5 to about 5 hr⁻¹.Typically, in the absence of a separation step, such as the separationmethod described herein, high-pressure hydrotreating at pressures ofabout 5,500 kPa to 12,000 kPa is necessary to reduce sulfur content andavoid catalyst poisoning by nitrogen-containing species. Advantageously,hydrotreating may be performed at a lower pressure of about 1300 kPa toabout 12,000 kPa (about 200 psig to about 1600 psig) if heteroatomspecies, such as nitrogen-containing species, are removed prior tohydrotreating via the separation methods described herein.

VI. FURTHER EMBODIMENTS

The invention can additionally or alternately include one or more of thefollowing embodiments.

Embodiment 1

An adsorbent material comprising: (i) a porous material support; and(ii) about 0.5 wt. % to about 30 wt. % of a Group 8 metal ion.

Embodiment 2

The adsorbent material of embodiment 1, wherein the porous materialsupport is selected from the group consisting of an organosilicamaterial, which is a polymer comprising independent units of a monomerof Formula [Z¹OZ²OSiCH₂]₃ (I), wherein Z¹ and Z² each independentlyrepresent a hydrogen atom, a C₁-C₄ alkyl group, or a bond to a siliconatom of another monomer; another siliceous material; and a combinationthereof.

Embodiment 3

The adsorbent material of embodiment 2, wherein Z¹ and Z² eachindependently represent a hydrogen atom, a C₁-C₂ alkyl group, or a bondto a silicon atom of another monomer.

Embodiment 4

The adsorbent material of embodiment 2 or 3, wherein Z¹ and Z² eachindependently represent a hydrogen atom, ethyl, or a bond to a siliconatom of another monomer.

Embodiment 5

The adsorbent material of any one of embodiments 2-4, wherein theorganosilica material further comprises at least one other monomerselected from the group consisting of:

-   -   (i) an independent unit of Formula [Z³OZ⁴SiCH₂]₃ (II), wherein        each Z³ represents a hydrogen atom, a C₁-C₄ alkyl group, or a        bond to a silicon atom of another monomer and Z⁴ represents a        C₁-C₆ alkyl group;    -   (ii) an independent unit of Formula Z⁵OZ⁶Z⁷Z⁸Si (III), wherein        each Z⁵ represents a hydrogen atom, a C₁-C₄ alkyl group, or a        bond to a silicon atom of another monomer; and Z⁶, Z⁷, and Z⁸        are each independently selected from the group consisting of a        hydroxyl group, a C₁-C₄ alkyl group, a C₁-C₄ alkoxy group, a        nitrogen-containing C₁-C₁₀ alkyl group, a nitrogen-containing        heteroalkyl group, a nitrogen-containing optionally substituted        heterocycloalkyl group, and an oxygen atom bonded to a silicon        atom of another monomer;    -   (iii) an independent unit of Formula Z⁹Z¹⁰Z¹¹Si—R—SiZ⁹Z¹⁰Z¹¹        (IV), wherein each Z⁹ independently represents a hydroxyl group,        a C₁-C₄ alkoxy group, or an oxygen atom bonded to a silicon atom        of another comonomer; each Z¹⁰ and Z¹¹ independently represent a        hydroxyl group, a C₁-C₄ alkoxy group, a C₁-C₄ alkyl group, or an        oxygen atom bonded to a silicon atom of another monomer; and R        is selected from the group consisting a C₁-C₈ alkylene group, a        C₂-C₈ alkenylene group, a C₂-C₈ alkynylene group, a        nitrogen-containing C₁-C₁₀ alkylene group, an optionally        substituted C₆-C₂₀ aralkyl, and an optionally substituted C₄-C₂₀        heterocycloalkyl group;    -   (iv) an independent cyclic polyurea monomer of Formula

-   -    wherein each R¹ independently is a X¹OX²X³SiX⁴ group, wherein        each X¹ represents a hydrogen atom, a C₁-C₄ alkyl group or a        bond to a silicon atom of another monomer unit; X² and X³ each        independently represent a hydroxyl group, a C₁-C₄ alkyl group, a        C₁-C₄ alkoxy group or an oxygen atom bonded to a silicon atom of        another monomer unit; and each X⁴ represents a C₁-C₈ alkylene        group bonded to a nitrogen atom of the cyclic polyurea.    -   (v) an independent unit of Formula M¹(OZ¹²)₃ (VI), wherein M¹        represents a Group 13 metal and each Z¹² independently        represents a hydrogen atom, a C₁-C₆ alkyl, or a bond to a        silicon atom of another monomer;    -   (vi) an independent unit of Formula (Z¹³O)₂M²-O—Si(OZ¹⁴)₃ (VII),        wherein M² represents a Group 13 metal and Z¹³ and Z¹⁴ each        independently represent a hydrogen atom, a C₁-C₆ alkyl group, or        a bond to a silicon atom of another monomer; and    -   (vii) a combination thereof.

Embodiment 6

The adsorbent material of embodiment 5, wherein at least one independentunit of Formula (II) is present, wherein each Z³ represents a hydrogenatom, a C₁-C₂ alkyl group, or a bond to a silicon atom of anothersiloxane monomer; and each Z⁴ represents a C₁-C₂ alkyl group.

Embodiment 7

The adsorbent material of embodiment 5 or 6, wherein each Z³ representsa hydrogen atom, ethyl, or a bond to a silicon atom of another siloxanemonomer; and each Z⁴ represents methyl.

Embodiment 8

The adsorbent material of any one of embodiments 5-7, wherein at leastone independent unit of Formula (III) is present, wherein each Z⁵represents a hydrogen atom, a C₁-C₂ alkyl group, or a bond to a siliconatom of another comonomer; and Z⁶, Z⁷, and Z⁸ are each independentlyselected from the group consisting of a hydroxyl group, a C₁-C₂ alkylgroup, C₁-C₂ alkoxy group, a nitrogen-containing C₃-C₁₀ alkyl group, anitrogen-containing C₄-C₁₀ heteroalkyl group, a nitrogen-containingoptionally substituted C₄-C₁₀ heterocycloalkyl group, and an oxygen atombonded to a silicon atom of another monomer.

Embodiment 9

The adsorbent material of any of embodiments 5-8, wherein each Z⁵represents a hydrogen atom, methyl, ethyl, or a bond to a silicon atomof another comonomer; and Z⁶, Z⁷, and Z⁸ are each independently selectedfrom the group consisting of a hydroxyl group, methyl, methoxy, ethoxy,

Embodiment 10

The adsorbent material of any one of embodiments 5-9, wherein at leastone independent unit of Formula (IV) is present, wherein each Z⁹represents a hydroxyl group, a C₁-C₂ alkoxy group, or an oxygen atombonded to a silicon atom of another comonomer; each Z¹⁰ and Z¹¹independently represent a hydroxyl group, a C₁-C₂ alkoxy group, a C₁-C₂alkyl group, or an oxygen atom bonded to a silicon atom of anothermonomer; and R is selected from the group consisting of a C₁-C₄ alkylenegroup, a C₂-C₄ alkenylene group, a C₂-C₄ alkynylene group, anitrogen-containing C₄-C₁₀ alkylene group, an optionally substitutedC₆-C₁₀ aralkyl and an optionally substituted C₄-C₁₂ heterocycloalkylgroup.

Embodiment 11

The adsorbent material of any one of embodiments 5-10, wherein each Z⁹represents a hydroxyl group, methoxy, ethoxy, or an oxygen atom bondedto a silicon atom of another comonomer; each Z¹⁰ and Z¹¹ independentlyrepresent a hydroxyl group, methoxy, ethoxy, methyl, or an oxygen atombonded to a silicon atom of another monomer; and R is selected from thegroup consisting of

Embodiment 12

The adsorbent material of any one of embodiments 5-11, wherein at leastone independent unit of Formula (V) is present, wherein each X¹represents a hydrogen atom, a C₁-C₂ alkyl group, or a bond to a siliconatom of another monomer unit; X² and X³ each independently represent ahydroxyl group, a C₁-C₂ alkyl group, a C₁-C₂ alkoxy group, or an oxygenatom bonded to a silicon atom of another monomer unit; and each X⁴represents a C₁-C₄ alkylene group bonded to a nitrogen atom of thecyclic compound.

Embodiment 13

The adsorbent material of any one of embodiments 5-12, wherein each X¹represents a hydrogen atom, methyl or a bond to a silicon atom ofanother monomer unit; X² and X³ each independently represent a hydroxylgroup, methoxy or an oxygen atom bonded to a silicon atom of anothermonomer unit and each X⁴ represents —CH₂CH₂CH₂— bonded to a nitrogenatom of the cyclic polyurea.

Embodiment 14

The adsorbent material of any one of embodiments 5-13, wherein at leastone independent unit of Formula (VI) is present, wherein M¹ is Al or Band each Z¹² independently represents a hydrogen atom, a C₁-C₄ alkylgroup, or a bond to a silicon atom or another monomer.

Embodiment 15

The adsorbent material of any one of embodiments 5-14, wherein at leastone independent unit of Formula (VII) is present, wherein M² is Al or Band Z¹³ and Z¹⁴ each independently represent a hydrogen atom, a C₁-C₄alkyl group, or a bond to a silicon atom of another monomer.

Embodiment 16

The adsorbent material of any one of embodiments 2-15, wherein theanother siliceous material is an amorphous silica.

Embodiment 17

The adsorbent material of embodiment 16, wherein the amorphous silica isa silica gel or MCM-41.

Embodiment 18

The adsorbent material of any one of the previous embodiments, whereinthe Group 8 metal ion is present in amount of about 1.0 wt. % to about15 wt. %.

Embodiment 19

The adsorbent material of any one of the previous embodiments, whereinthe Group 8 metal ion is ferrous iron, ferric iron or a combinationthereof.

Embodiment 20

A method of making an adsorbent material, the method comprising:

(a) impregnating a porous material support with a Group 8 metal ion,wherein the porous material comprises between about 0.5 wt. % to about30 wt. % of the Group 8 metal ion; and

(b) drying the impregnated porous material support.

Embodiment 21

The method of embodiment 20, wherein impregnating comprises spraying theporous material support with an aqueous solution of the Group 8 metalion.

Embodiment 22

The method of embodiment 20 or 21, wherein the porous material comprisesbetween about 1.0 wt. % to about 15 wt. % of the Group 8 metal ion.

Embodiment 23

The method of any one of embodiments 20-23, wherein Group 8 metal ion isprovided by a Group 8 metal salt.

Embodiment 24

The method of any one of embodiments 20-23, wherein the Group 8 metalion is ferrous iron, ferric iron or a combination thereof.

Embodiment 25

The method of any one of embodiments 20-24, wherein the drying occurs ata temperature between about 100° C. and 130° C.

Embodiment 26

The method of any one of embodiments 20-25, wherein the porous materialsupport is selected from the group consisting of an organosilicamaterial, which is a polymer comprising independent units of a monomerof Formula [Z¹OZ²OSiCH₂]₃ (I), wherein Z¹ and Z² each independentlyrepresent a hydrogen atom, a C₁-C₄ alkyl group, or a bond to a siliconatom of another monomer; another siliceous material; and a combinationthereof.

Embodiment 27

The method of embodiment 26, wherein Z¹ and Z² each independentlyrepresent a hydrogen atom, a C₁-C₂ alkyl group, or a bond to a siliconatom of another monomer.

Embodiment 28

The method of embodiment 26 or 27, wherein Z¹ and Z² each independentlyrepresent a hydrogen atom, ethyl, or a bond to a silicon atom of anothermonomer.

Embodiment 29

The method of embodiments 26-28, wherein the organosilica materialfurther comprises at least one other monomer selected from the groupconsisting of:

-   -   (i) an independent unit of Formula [Z³OZ⁴SiCH₂]₃ (II), wherein        each Z³ represents a hydrogen atom, a C₁-C₄ alkyl group, or a        bond to a silicon atom of another monomer and each Z⁴ represents        a C₁-C₆ alkyl group;    -   (ii) an independent unit of Formula Z⁵OZ⁶Z⁷Z⁸Si (III), wherein        each Z⁵ represents a hydrogen atom, a C₁-C₄ alkyl group, or a        bond to a silicon atom of another monomer; and Z⁶, Z⁷, and Z⁸        are each independently selected from the group consisting of a        hydroxyl group, a C₁-C₄ alkyl group, a C₁-C₄ alkoxy group, a        nitrogen-containing C₁-C₁₀ alkyl group, a nitrogen-containing        heteroalkyl group, a nitrogen-containing optionally substituted        heterocycloalkyl group, and an oxygen atom bonded to a silicon        atom of another monomer;    -   (iii) an independent unit of Formula Z⁹Z¹⁰Z¹¹Si—R—SiZ⁹Z¹⁰Z¹¹        (IV), wherein each Z⁹ independently represents a hydroxyl group,        a C₁-C₄ alkoxy group, or an oxygen atom bonded to a silicon atom        of another comonomer; each Z¹⁰ and Z¹¹ independently represent a        hydroxyl group, a C₁-C₄ alkoxy group, a C₁-C₄ alkyl group, or an        oxygen atom bonded to a silicon atom of another monomer; and R        is selected from the group consisting a C₁-C₈ alkylene group, a        C₂-C₈ alkenylene group, a C₂-C₈ alkynylene group, a        nitrogen-containing C₁-C₁₀ alkylene group, an optionally        substituted C₆-C₂₀ aralkyl, and an optionally substituted C₄-C₂₀        heterocycloalkyl group;    -   (iv) an independent cyclic polyurea monomer of Formula

-   -    wherein each R¹ independently is a X¹OX²X³SiX⁴ group, wherein        each X¹ represents a hydrogen atom, a C₁-C₄ alkyl group or a        bond to a silicon atom of another monomer unit; X² and X³ each        independently represent a hydroxyl group, a C₁-C₄ alkyl group, a        C₁-C₄ alkoxy group or an oxygen atom bonded to a silicon atom of        another monomer unit; and each X⁴ represents a C₁-C₈ alkylene        group bonded to a nitrogen atom of the cyclic polyurea.    -   (v) an independent unit of Formula M¹(OZ¹²)₃ (VI), wherein M¹        represents a Group 13 metal and each Z¹² independently        represents a hydrogen atom, a C₁-C₆ alkyl, or a bond to a        silicon atom of another monomer;    -   (vi) an independent unit of Formula (Z¹³O)₂M²-O—Si(OZ¹⁴)₃ (VII),        wherein M² represents a Group 13 metal and Z¹³ and Z¹⁵ each        independently represent a hydrogen atom, a C₁-C₆ alkyl group, or        a bond to a silicon atom of another monomer; and    -   (vii) a combination thereof.

Embodiment 30

The method of embodiment 29, wherein at least one independent unit ofFormula (II) is present, wherein each Z³ represents a hydrogen atom, aC₁-C₂ alkyl group, or a bond to a silicon atom of another siloxanemonomer; and each Z⁴ represents a C₁-C₂ alkyl group.

Embodiment 31

The method of embodiment 29 or 30, wherein each Z³ represents a hydrogenatom, ethyl, or a bond to a silicon atom of another siloxane monomer;and each Z⁴ represents methyl.

Embodiment 32

The method of any one of embodiments 29-31, wherein at least one unit ofFormula (III) is present, wherein each Z⁵ represents a hydrogen atom, aC₁-C₂ alkyl group, or a bond to a silicon atom of another comonomer; andZ⁶, Z⁷, and Z⁸ are each independently selected from the group consistingof a hydroxyl group, a C₁-C₂ alkyl group, C₁-C₂ alkoxy group, anitrogen-containing C₃-C₁₀ alkyl group, a nitrogen-containing C₄-C₁₀heteroalkyl group, a nitrogen-containing optionally substituted C₄-C₁₀heterocycloalkyl group, and an oxygen atom bonded to a silicon atom ofanother monomer.

Embodiment 33

The method of any one of embodiments 29-32, wherein each Z⁵ represents ahydrogen atom, methyl, ethyl, or a bond to a silicon atom of anothercomonomer; and Z⁶, Z⁷, and Z⁸ are each independently selected from thegroup consisting of a hydroxyl group, methyl, methoxy, ethoxy,

Embodiment 34

The method of any one of embodiments 29-33, wherein at least oneindependent unit of Formula (IV) is present, wherein each Z⁹ representsa hydroxyl group, a C₁-C₂ alkoxy group, or an oxygen atom bonded to asilicon atom of another comonomer; each Z¹⁰ and Z¹¹ independentlyrepresent a hydroxyl group, a C₁-C₂ alkoxy group, a C₁-C₂ alkyl group,or an oxygen atom bonded to a silicon atom of another monomer; and R isselected from the group consisting of a C₁-C₄ alkylene group, a C₂-C₄alkenylene group, a C₂-C₄ alkynylene group, a nitrogen-containing C₄-C₁₀alkylene group, an optionally substituted C₆-C₁₀ aralkyl and anoptionally substituted C₄-C₁₂ heterocycloalkyl group.

Embodiment 35

The method of any one of embodiments 29-34, wherein each Z⁹ represents ahydroxyl group, methoxy, ethoxy, or an oxygen atom bonded to a siliconatom of another comonomer; each Z¹⁰ and Z¹¹ independently represent ahydroxyl group, methoxy, ethoxy, methyl, or an oxygen atom bonded to asilicon atom of another monomer; and R is selected from the groupconsisting of —CH₂—, —CH₂CH₂—, —HC═CH—,

Embodiment 36

The method of any one of embodiments 29-35, wherein at least oneindependent unit of Formula (V) is present, wherein each X¹ represents ahydrogen atom, a C₁-C₂ alkyl group, or a bond to a silicon atom ofanother monomer unit; X² and X³ each independently represent a hydroxylgroup, a C₁-C₂ alkyl group, a C₁-C₂ alkoxy group, or an oxygen atombonded to a silicon atom of another monomer unit; and each X⁴ representsa C₁-C₄ alkylene group bonded to a nitrogen atom of the cyclic compound.

Embodiment 37

The method of claim of any one of embodiments 29-36, wherein each X¹represents a hydrogen atom, methyl or a bond to a silicon atom ofanother monomer unit; X² and X³ each independently represent a hydroxylgroup, methoxy or an oxygen atom bonded to a silicon atom of anothermonomer unit and each X⁴ represents —CH₂CH₂CH₂— bonded to a nitrogenatom of the cyclic polyurea.

Embodiment 38

The method of any one of embodiments 29-37, wherein at least oneindependent unit of Formula (VI) is present, wherein M¹ is Al or B andeach Z¹² represents a hydrogen atom, a C₁-C₄ alkyl group, or a bond to asilicon atom or another monomer.

Embodiment 39

The method of any one of embodiments 29-38, wherein at least oneindependent unit of Formula (VII) is present, wherein M² is Al or B andZ¹³ and Z¹⁴ each independently represent a hydrogen atom, a C₁-C₄ alkylgroup, or a bond to a silicon atom of another monomer.

Embodiment 40

The method of any one of embodiments 26-39, wherein the organosilicamaterial is made using substantially no structure directing agent orporogen.

Embodiment 41

The method of any one of embodiments 26-40, wherein the anothersiliceous material is an amorphous silica.

Embodiment 42

The method of embodiment 41, wherein the amorphous silica is a silicagel or MCM-41.

Embodiment 43

An adsorbent material made by the method of any one of embodiments 20-42

Embodiment 44

A method of separating a heteroatom species from a hydrocarbonfeedstream, the method comprising contacting the hydrocarbon feedstreamcontaining at least one heteroatom species with the adsorbent materialof any one of embodiments 1-19.

Embodiment 45

The method of embodiment 45, wherein the heteroatom species is selectedfrom the group consisting of a nitrogen-containing species, asulfur-containing species, an oxygen-containing species, and acombination thereof.

Embodiment 46

The method of embodiment 44 or 45, wherein the heteroatom speciescomprises nitrogen-containing species or sulfur-containing species.

Embodiment 47

The method of embodiment 45 or 46, wherein at least about 20% of thenitrogen-containing species are separated from the hydrocarbonfeedstream.

Embodiment 48

The method of embodiment 45 or 46, wherein at least about 10% of thesulfur-containing species are separated from the hydrocarbon feedstream.

Embodiment 49

The method of any one of embodiments 44-48, wherein the hydrocarbonfeedstream is selected from the group consisting of whole crude, lightgas oil (LGO), light cycle oil (LCO), and virgin diesel.

Embodiment 50

The method of any one of embodiments 44-49 further comprisinghydrotreating the hydrocarbon feedstream.

Embodiment 51

The method of embodiment 50, wherein hydrotreating is performed at ahydrogen pressure of about 200 psig to about 1600 psig.

EXAMPLES

The following examples are merely illustrative, and do not limit thisdisclosure in any way.

General Methods Nitrogen Porosimetry

The nitrogen adsorption/desorption analyses was performed with differentinstruments, e.g. TriStar 3000, TriStar II 3020 and Autosorb-1. All thesamples were pre-treated at 120° C. in vacuum for 4 hours beforecollecting the N₂ isotherm. The analysis program calculated theexperimental data and report BET surface area (total surface area),microporous surface area (S), total pore volume, pore volume formicropores, average pore diameter (or radius), etc.

Example 1 Synthesis and Preparation of Amorphous Silicas and MesoporousOrganosilicas (MO) without FeCl₃ Impregnation 1.A. Comparative N₂Calcined MCM-41A-D and Air Calcined MCM-41A-D:

All MCM-41 materials used in these tests were synthesized according tomethods disclosed in U.S. Pat. Nos. 5,098,684; 5,102,643; or 5,108,725

Resulting material from these methods is referred to as wet cake, i.e.mesoporous silica containing organic surfactant and water. Pore size,surface area (determined by nitrogen adsorption/desorption analysis) andSi:Al₂ ratios of the materials is shown below in Table 1.

TABLE 1 Pore Size (Å) Si:Al₂ Surface Area (m²/g) MCM-41A 40 50 900MCM-41B 50 50 800 MCM-41C 40 >600 900 MCM-41D 25 50 1400

Preparation of N₂ Calcined MCM-41A-D:

-   -   1. 400 g of wet cake (i.e. MCM-41A-D) was placed inside        ventilated furnace.    -   2. Nitrogen purge at 1 L/min was established.    -   3. Furnace was heated to 1000° F. at a ramp rate ranging from        1-20° C./min.    -   4. Wet cake was calcined under nitrogen flow for 3 hours at        1000° F.    -   5. Wet cake was cooled to room temperature (20-25° C.) and        discharged to obtain the following: N₂ Calcined MCM-41A, N₂        Calcined MCM-41B, N₂ Calcined MCM-41C and N₂ Calcined MCM-41D.

Preparation of Air Calcined MCM-41 A-D:

-   -   1. 100 g of N₂ calcined MCM-41A-D was placed inside a ventilated        furnace.    -   2. Air flow was established at 250 cc/min.    -   3. Furnace was heated to 1000° F. at a ramp rate ranging from        1-20° C./min    -   4. Material was calcined in air flow for 3 hours at 1000° F.    -   5. Material was cooled to room temperature (20-25° C.) and        discharged to obtain the following: Air Calcined MCM-41A, Air        Calcined MCM-41B, Air Calcined MCM-41C and Air Calcined MCM-41D.        1.B. Synthesis of MO Using [(EtO)₂SiCH₂]₃ in Basic Aqueous        Medium

A solution with 31.1 g of 30% NH₄OH and 39.9 g deionized water (DI)water was made. The pH of the solution was 12.55. To the solution, 20 gof [(EtO)₂SiCH₂]₃ was added, producing a mixture having the molarcomposition:

-   -   1.0 [(EtO)2SiCH2]3:21 OH:270 H₂O

The solution was stirred for 1 day at room temperature (20-25° C.). Thesolution was transferred to an autoclave and aged at 90° C. for 1 day toproduce a gel. The gel was dried at 120° C. in a vacuum oven for 1 day(16-24 hours). This produced Comparative MO as a clear solid whichbecame a white powder after grinding. No surface directing agent orporogen were used in this preparation. The pore size and surface area ofthe Comparative MO, Norit RX-3 (obtained from Cabot Corporation) andSorbonit-4 (obtained from Cabot Corporation) as determined by nitrogenadsorption/desorption analysis) is shown below in Table 2.

TABLE 2 Pore Size (Å) Surface Area (m²/g) Comparative MO 35 1300 NoritRX-3 39 1200 Sorbonit-4 46 15001.C. Synthesis of Comparative TEOS-MO Using [(EtO)₂SiCH₂]₃ and TEOS(Tetraethylorthosilicate)

A solution with 31.5 g of 30% NH₄OH (265 mmol NH₄OH) and 39.9 g DI waterwas made. To the solution, 4 g (10 mmol) of [(EtO)₂SiCH₂]₃ and 3.125 g(15 mmoles) of TEOS was added to produce a solution having the molarcomposition:

-   -   2.0 [(EtO)₂SiCH₂]₃: 3.0 TEOS:53 OH:682 H₂O        which was stirred for 1 day at room temperature (20-25° C.). The        solution was transferred to an autoclave and aged at 90° C. for        1 day to produce a gel. The gel was dried in a vacuum at 120° C.        overnight (16-24 hours) and Comparative TEOS-MO was obtained. No        structure directing agent or porogen were used.

Example 2 Preparation of FeCl₃/CuCl₂ Impregnated Amorphous Silicas andMOs 2A. Synthesis of FeCl₃ Impregnated MO

A solution of 10 wt. % of FeCl₃ (obtained from Sigma-Aldrich) wasprepared by dissolving 1.665 g FeCl₃.6H₂O into 8.335 g DI water.Comparative MO (4.5 g) was mixed with 5.4 ml of the solution to form amixture. The mixture was stirred and then the solid was dried at 120° C.in an oven under vacuum overnight (16-24 hours) to obtain Fe³⁺-MO.

2B. Synthesis of FeCl₃ Impregnated TEOS-MO

A solution of 10 wt. % of FeCl₃ (obtained from Sigma-Aldrich) was madeby dissolving 1.665 g FeCl₃.6H₂O into 8.335 g DI water. The aboveComparative TEOS-MO (1 g) was mixed with 1.2 ml of the solution to forma mixture. The mixture was stirred, and then the solid was dried at 120°C. in an oven under vacuum overnight (16-24 hours) to obtainFe³⁺-TEOS-MO.

2C. Synthesis of CuCl₂ Impregnated TEOS-MO

A solution of 20 wt. % of CuCl₂ (obtained from Sigma-Aldrich) was made.Then, the above Comparative TEOS-MO (1 g) was mixed with 1.2 ml of thesolution to form a mixture. The mixture was stirred and then the solidwas dried in an oven under vacuum at 120° C. overnight (16-24 hours) toobtain Cu²⁺-TEOS-MO.

2D. Preparation of FeCl₃ Impregnated Commercially Available AmorphousSilicas (Davisil 635, Davisil 646, Evonik 4210)

-   -   1. 20 g of silica was ball milled for 24 hours to reduce        particle size to 10-30 microns diameter.    -   2. Stock solutions of either 10 wt. % or 20 wt. % or 30 wt. % of        FeCl₃ were prepared (Reagent Grade, 97% purity, Sigma Aldrich),        by dissolving 2 g, or 4 g, or 6 g, of FeCl₃ salt in 20 cc of        deionized water. Higher concentrations were needed for higher        wt. % of FeCl₃ on support.    -   3. Water absorption of the ground silica was measured and the        stock solution of FeCl₃ was diluted with DI water to match 95%        of the absorption capacity. The procedure for measuring water        adsorption was as follows:        -   a. Water absorption capacity was measured by:            -   i. Weighing dry support (silica or MO)            -   ii. Slowly spraying water until the support was visibly                saturated (no more taken up by sorbate)            -   iii. Weighing the wetted support        -   b. Water absorption capacity was calculated using the            following formula:

$\text{Water Absorption Capacity =}\frac{\text{wet weight} - \text{dry weight}}{\text{dry weight}}$

-   -   4. The appropriate amount of solution (according to Table 2        below) was sprayed onto the support using a pill coater:        -   a. Rotation speed of the coater was adjusted to 30 RPM        -   b. The solution was sprayed onto the support with a pipetter            over the course of 10 min while maintaining the rotation        -   c. After all solution was delivered, rotation tumbling            continued for another 20 min at 10 RPM    -   5. The supports were dried overnight in an oven at 250° F. under        nitrogen atmosphere.

The amount and wt. % of each stock solution used for Davisil 646(obtained from Sigma Aldrich), Davisil 635 (obtained from Sigma Aldrich)and Evonik 4210 (obtained from Evonik) are shown below in Table 3.

TABLE 3 Spray Solution Stock Weight Weight Components Solution of ofWeight of DI Used Silica Spray Stock water Fe3+ (% Support SolutionSolution Used makeup (wt. %) FeCl₃) (g) (g) (g) (g) Davisil 1 10 10 10.52.9 7.6 646 3 10 10 10.7 8.7 2.0 6 20 10 10.7 8.7 2.0 10 30 10 10.7 9.71.0 Davisil 1 10 10 9.2 2.9 6.3 635 Evonik 6 20 30 29.3 26.2 3.2 4210

Example 3 Heteroatom Species Removal from Refinery Streams GeneralProcedure

The procedure for nitrogen and sulfur species removal was as follows:

-   -   1. 1 gram of adsorbent (e.g. Fe³⁺-MO) was charged into a clear        20 cc bottle, with a cap.    -   2. 10 ml of the feed (e.g. LGO) was added and stirred with a        magnetic stirrer for 24 hours.    -   3. Solids were separated from supernatant by centrifugation.    -   4. The top layer was collected with a suction pipette.    -   5. Total nitrogen (and sulfur) analysis using chemiluminescence        method as measured by an Antek instrument was performed on the        sample.

The adsorbents were tested at room temperature (20-25° C.) andatmospheric pressure (1 atm). Tests were done at 10:1 feed:adsorbentratio.

3A. Removal of Nitrogen From Virgin Diesel

FIGS. 1 and 2 show nitrogen removal (total remaining and % remaining)from virgin diesel using the following materials: Ground Up Davisil 646,Ball-Milled Davisil 646 w/ 3% Fe³⁺, Ball-Milled Davisil 646 w/ 6% Fe³⁺and Ball-Milled Davisil 646 w/ 10% Fe³⁺. The adsorbents reduced nitrogencontent from 100 ppm to about 13 ppm or by about 87%.

FIGS. 3 and 4 show nitrogen removal (total remaining and % remaining)from virgin diesel using the following materials: Ground Up Davisil 646,Ball-Milled Davisil 646 w/ 3% Fe³⁺, Ball-Milled Davisil 646 w/ 10% Fe³⁺,Comparative TEOS-MO, Comparative MO (1^(st)-3^(rd) runs),) Cu²⁺-TEOS-MOand Fe³⁺-TEOS-MO. The adsorbents reduced nitrogen content from 100 ppmto about 9 ppm or about 90%.

FIGS. 5 and 6 show nitrogen removal (total remaining and % remaining)from virgin diesel using the following materials: Ground Up Davisil 646,Ball-Milled Davisil 646 w/ 3% Fe³⁺, Ball-Milled Davisil 646 w/ 10% Fe³⁺,Comparative TEOS-MO, Comparative MO (1^(st)-3^(rd) runs),) Cu²⁺-TEOS-MO,Fe³⁺-TEOS-MO, N₂ Calcined MCM-41A, N₂ Calcined MCM-41B, N₂ CalcinedMCM-41C, N₂ Calcined MCM-41D, Air Calcined MCM-41A, Air CalcinedMCM-41B, Air Calcined MCM-41C and Air Calcined MCM-41D. The adsorbentsreduced nitrogen content from 350 ppm to about 65 ppm or about 80%.

3B. Removal of Sulfur From Virgin Diesel

FIGS. 7 and 8 show sulfur removal (wt. % and ppm) from virgin dieselusing the following materials: Comparative MO (1^(st) run), N₂ CalcinedMCM-41A, N₂ Calcined MCM-41B, N₂ Calcined MCM-41C, N₂ Calcined MCM-41D,Air Calcined MCM-41A, Air Calcined MCM-41B, Air Calcined MCM-41C and AirCalcined MCM-41D.

3C. Removal of Nitrogen From Light Gas Oil (LGO)

FIGS. 9 and 10 show nitrogen removal (total remaining and % remaining)from Fawley LGO using the following materials: Ball Milled Davisil 646,Ball Milled Davisil 635, Davisil 635 w/ 1% Fe³⁺, Davisil 646 w/ 1% Fe³⁺,Davisil 646 w/ 3% Fe³⁺, Davisil 646 w/ 6% Fe³⁺ and Davisil 646 w/ 10%Fe³⁺. The adsorbents reduced nitrogen content from 250 ppm to about 60ppm or about 77%.

FIGS. 11 and 12 show nitrogen removal (total remaining and % remaining)from Fawley LGO using the following materials: Ball Milled Davisil 646,Ball Milled Davisil 635, Davisil 646 w/ 3% Fe³⁺, Fe³⁺-TEOS-MO, NoritRX-3 and Sorbonit-4. The adsorbents reduced nitrogen content from 250ppm to about 23 ppm or about 90%.

3D. Removal of Nitrogen From Light Cycle Oil (LCO)

FIGS. 13 and 14 show nitrogen removal (total remaining and % remaining)from Fawley LCO using the following materials: Ball Milled Davisil 646,Ball Milled Davisil 646 w/ 1% Fe³⁺, Ball Milled Davisil 646 w/ 3% Fe³⁺,Ball Milled Davisil 646 w/ 6% Fe³⁺ and Ball Milled Davisil 646 w/ 10%Fe³⁺. The adsorbents reduced nitrogen content from 1500 ppm to about 730ppm or about 52%.

FIGS. 15 and 16 show nitrogen removal (total remaining and % remaining)from Fawley LCO using the following materials: Ball Milled Davisil 646,Ball Milled Davisil 646 w/ 3% Fe³⁺ and Fe³⁺-TEOS-MO. The adsorbentsreduced nitrogen content from 1500 ppm to about 600 ppm or about 60%.

FIGS. 17 and 18 show nitrogen removal (total remaining and % remaining)from Joliet LCO using the following materials: Davisil 646, Davisil 646w/ 1% Fe³⁺, Davisil 646 w/ 3% Fe³⁺ and Evonik 4210 w/ 6% Fe³⁺. Theadsorbents reduced nitrogen content from 1150 ppm to about 900 ppm orabout 25%.

FIGS. 19 and 20 show nitrogen removal (total remaining and % remaining)from Joliet LCO using the following materials: Davisil 646, Davisil 646w/ 3% Fe³⁺ and Fe³⁺-TEOS-MO. The adsorbents reduced nitrogen contentfrom 1150 ppm to about 750 ppm or about 25%.

FIGS. 21 and 22 show nitrogen removal (total remaining and % remaining)from Chiba LCO using the following materials: Davisil 635 w/ 1% Fe³⁺ andFe³⁺-TEOS-MO. The adsorbents reduced nitrogen content from 180 ppm toabout 70 ppm or about 40%.

3E. Removal of Nitrogen From Arabian Extra Light Crude

FIGS. 23 and 24 show nitrogen removal (total remaining and % remaining)from Arabian Extra Light Crude using the following materials: Davisil646 w/ 3% Fe³⁺ and Davisil 646 w/ 6% Fe³⁺. The adsorbents reducednitrogen content from 350 ppm to about 100 ppm or about 70%.

FIGS. 25 and 26 show nitrogen removal (total remaining and % remaining)from Arabian Light Extra Crude using the following materials: Davisil646 w/ 3% Fe³⁺, Comparative MO and Fe³⁺-TEOS-MO. The adsorbents reducednitrogen content from 350 ppm to about 65 ppm or about 80%.

What is claimed is:
 1. An adsorbent material comprising: (i) a porousmaterial support; and (ii) about 0.5 wt. % to about 30 wt. % of a Group8 metal ion.
 2. The adsorbent material of claim 1, wherein the porousmaterial support is selected from the group consisting of anorganosilica material, which is a polymer comprising independent unitsof a monomer of Formula [Z¹OZ²OSiCH₂]₃ (I), wherein Z¹ and Z² eachindependently represent a hydrogen atom, a C₁-C₄ alkyl group, or a bondto a silicon atom of another monomer; another siliceous material; and acombination thereof.
 3. The adsorbent material of claim 2, wherein Z¹and Z² each independently represent a hydrogen atom, a C₁-C₂ alkylgroup, or a bond to a silicon atom of another monomer.
 4. The adsorbentmaterial of claim 2, wherein Z¹ and Z² each independently represent ahydrogen atom, ethyl, or a bond to a silicon atom of another monomer. 5.The adsorbent material of claim 2, wherein the organosilica materialfurther comprises at least one other monomer selected from the groupconsisting of: (i) an independent unit of Formula [Z³OZ⁴SiCH₂]₃ (II),wherein each Z³ represents a hydrogen atom, a C₁-C₄ alkyl group, or abond to a silicon atom of another monomer and Z⁴ represents a C₁-C₆alkyl group; (ii) an independent unit of Formula Z⁵OZ⁶Z⁷Z⁸Si (III),wherein each Z⁵ represents a hydrogen atom, a C₁-C₄ alkyl group, or abond to a silicon atom of another monomer; and Z⁶, Z⁷, and Z⁸ are eachindependently selected from the group consisting of a hydroxyl group, aC₁-C₄ alkyl group, a C₁-C₄ alkoxy group, a nitrogen-containing C₁-C₁₀alkyl group, a nitrogen-containing heteroalkyl group, anitrogen-containing optionally substituted heterocycloalkyl group, andan oxygen atom bonded to a silicon atom of another monomer; (iii) anindependent unit of Formula Z⁹Z¹⁰Z¹¹Si—R—SiZ⁹Z¹⁰Z¹¹ (IV), wherein eachZ⁹ independently represents a hydroxyl group, a C₁-C₄ alkoxy group, oran oxygen atom bonded to a silicon atom of another comonomer; each Z¹⁰and Z¹¹ independently represent a hydroxyl group, a C₁-C₄ alkoxy group,a C₁-C₄ alkyl group, or an oxygen atom bonded to a silicon atom ofanother monomer; and R is selected from the group consisting a C₁-C₈alkylene group, a C₂-C₈ alkenylene group, a C₂-C₈ alkynylene group, anitrogen-containing C₁-C₁₀ alkylene group, an optionally substitutedC₆-C₂₀ aralkyl, and an optionally substituted C₄-C₂₀ heterocycloalkylgroup; (iv) an independent cyclic polyurea monomer of Formula

 wherein each R¹ independently is a X¹OX²X³SiX⁴ group, wherein each X¹represents a hydrogen atom, a C₁-C₄ alkyl group or a bond to a siliconatom of another monomer unit; X² and X³ each independently represent ahydroxyl group, a C₁-C₄ alkyl group, a C₁-C₄ alkoxy group or an oxygenatom bonded to a silicon atom of another monomer unit; and each X⁴represents a C₁-C₈ alkylene group bonded to a nitrogen atom of thecyclic polyurea. (v) an independent unit of Formula M¹(OZ¹²)₃ (VI),wherein M¹ represents a Group 13 metal and each Z¹² independentlyrepresents a hydrogen atom, a C₁-C₆ alkyl, or a bond to a silicon atomof another monomer; (vi) an independent unit of Formula(Z¹³O)₂M²-O—Si(OZ¹⁴)₃ (VII), wherein M² represents a Group 13 metal andZ¹³ and Z¹⁴ each independently represent a hydrogen atom, a C₁-C₆ alkylgroup, or a bond to a silicon atom of another monomer; and (vii) acombination thereof.
 6. The adsorbent material of claim 5, wherein atleast one independent unit of Formula (II) is present, wherein each Z³represents a hydrogen atom, a C₁-C₂ alkyl group, or a bond to a siliconatom of another siloxane monomer; and each Z⁴ represents a C₁-C₂ alkylgroup.
 7. The adsorbent material of claim 6, wherein each Z³ representsa hydrogen atom, ethyl, or a bond to a silicon atom of another siloxanemonomer; and each Z⁴ represents methyl.
 8. The adsorbent material ofclaim 5, wherein at least one independent unit of Formula (III) ispresent, wherein each Z⁵ represents a hydrogen atom, a C₁-C₂ alkylgroup, or a bond to a silicon atom of another comonomer; and Z⁶, Z⁷, andZ⁸ are each independently selected from the group consisting of ahydroxyl group, a C₁-C₂ alkyl group, C₁-C₂ alkoxy group, anitrogen-containing C₃-C₁₀ alkyl group, a nitrogen-containing C₄-C₁₀heteroalkyl group, a nitrogen-containing optionally substituted C₄-C₁₀heterocycloalkyl group, and an oxygen atom bonded to a silicon atom ofanother monomer.
 9. The adsorbent material of claim 8, wherein each Z⁵represents a hydrogen atom, methyl, ethyl, or a bond to a silicon atomof another comonomer; and Z⁶, Z⁷, and Z⁸ are each independently selectedfrom the group consisting of a hydroxyl group, methyl, methoxy, ethoxy,


10. The adsorbent material of claim 5, wherein at least one independentunit of Formula (IV) is present, wherein each Z⁹ represents a hydroxylgroup, a C₁-C₂ alkoxy group, or an oxygen atom bonded to a silicon atomof another comonomer; each Z¹⁰ and Z¹¹ independently represent ahydroxyl group, a C₁-C₂ alkoxy group, a C₁-C₂ alkyl group, or an oxygenatom bonded to a silicon atom of another monomer; and R is selected fromthe group consisting of a C₁-C₄ alkylene group, a C₂-C₄ alkenylenegroup, a C₂-C₄ alkynylene group, a nitrogen-containing C₄-C₁₀ alkylenegroup, an optionally substituted C₆-C₁₀ aralkyl and an optionallysubstituted C₄-C₁₂ heterocycloalkyl group.
 11. The adsorbent material ofclaim 10, wherein each Z⁹ represents a hydroxyl group, methoxy, ethoxy,or an oxygen atom bonded to a silicon atom of another comonomer; eachZ¹⁰ and Z¹¹ independently represent a hydroxyl group, methoxy, ethoxy,methyl, or an oxygen atom bonded to a silicon atom of another monomer;and R is selected from the group consisting of —CH₂—, —CH₂CH₂—, HC═CH—,


12. The adsorbent material of claim 5, wherein at least one independentunit of Formula (V) is present, wherein each X¹ represents a hydrogenatom, a C₁-C₂ alkyl group, or a bond to a silicon atom of anothermonomer unit; X² and X³ each independently represent a hydroxyl group, aC₁-C₂ alkyl group, a C₁-C₂ alkoxy group, or an oxygen atom bonded to asilicon atom of another monomer unit; and each X⁴ represents a C₁-C₄alkylene group bonded to a nitrogen atom of the cyclic compound.
 13. Theadsorbent material of claim 12, wherein each X¹ represents a hydrogenatom, methyl or a bond to a silicon atom of another monomer unit; X² andX³ each independently represent a hydroxyl group, methoxy or an oxygenatom bonded to a silicon atom of another monomer unit and each X⁴represents —CH₂CH₂CH₂— bonded to a nitrogen atom of the cyclic polyurea.14. The adsorbent material of claim 5, wherein at least one independentunit of Formula (VI) is present, wherein M¹ is Al or B and each Z¹²independently represents a hydrogen atom, a C₁-C₄ alkyl group, or a bondto a silicon atom or another monomer.
 15. The adsorbent material ofclaim 5, wherein at least one independent unit of Formula (VII) ispresent, wherein M² is Al or B and Z¹³ and Z¹⁴ each independentlyrepresent a hydrogen atom, a C₁-C₄ alkyl group, or a bond to a siliconatom of another monomer.
 16. The adsorbent material of claim 2, whereinthe another siliceous material is an amorphous silica.
 17. The adsorbentmaterial of claim 16, wherein the amorphous silica is a silica gel orMCM-41.
 18. The adsorbent material of claim 1, wherein the Group 8 metalion is present in amount of about 1.0 wt. % to about 15 wt. %.
 19. Theadsorbent material of claim 1, wherein the Group 8 metal ion is ferrousiron, ferric iron or a combination thereof.
 20. A method of making anadsorbent material, the method comprising: (a) impregnating a porousmaterial support with a Group 8 metal ion, wherein the porous materialcomprises between about 0.5 wt % to about 30 wt % of the Group 8 metalion; and (b) drying the impregnated porous material support.
 21. Themethod of claim 20, wherein impregnating comprises spraying the porousmaterial support with an aqueous solution of the Group 8 metal ion. 22.The method of claim 20, wherein the porous material comprises betweenabout 1.0 wt. % to about 15 wt. % of the Group 8 metal ion.
 23. Themethod of claim 20, wherein Group 8 metal ion is provided by a Group 8metal salt.
 24. The method of claim 20, wherein the Group 8 metal ion isferrous iron, ferric iron or a combination thereof.
 25. The method ofclaim 20, wherein the drying occurs at a temperature between about 100°C. and 130° C.
 26. The method of claim 20, wherein the porous materialsupport is selected from the group consisting of an organosilicamaterial, which is a polymer comprising independent units of a monomerof Formula [Z¹OZ²OSiCH₂]₃ (I), wherein Z¹ and Z² each independentlyrepresent a hydrogen atom, a C₁-C₄ alkyl group, or a bond to a siliconatom of another monomer; another siliceous material; and a combinationthereof.
 27. The method of claim 26, wherein Z¹ and Z² eachindependently represent a hydrogen atom, a C₁-C₂ alkyl group, or a bondto a silicon atom of another monomer.
 28. The method of claim 27,wherein Z¹ and Z² each independently represent a hydrogen atom, ethyl,or a bond to a silicon atom of another monomer.
 29. The method of claim26, wherein the organosilica material further comprises at least oneother monomer selected from the group consisting of: (i) an independentunit of Formula [Z³OZ⁴SiCH₂]₃ (II), wherein each Z³ represents ahydrogen atom, a C₁-C₄ alkyl group, or a bond to a silicon atom ofanother monomer and each Z⁴ represents a C₁-C₆ alkyl group; (ii) anindependent unit of Formula Z⁵OZ⁶Z⁷Z⁸Si (III), wherein each Z⁵represents a hydrogen atom, a C₁-C₄ alkyl group, or a bond to a siliconatom of another monomer; and Z⁶, Z⁷, and Z⁸ are each independentlyselected from the group consisting of a hydroxyl group, a C₁-C₄ alkylgroup, a C₁-C₄ alkoxy group, a nitrogen-containing C₁-C₁₀ alkyl group, anitrogen-containing heteroalkyl group, a nitrogen-containing optionallysubstituted heterocycloalkyl group, and an oxygen atom bonded to asilicon atom of another monomer; (iii) an independent unit of FormulaZ⁹Z¹⁰Z¹¹Si—R—SiZ⁹Z¹⁰Z¹¹ (IV), wherein each Z⁹ independently represents ahydroxyl group, a C₁-C₄ alkoxy group, or an oxygen atom bonded to asilicon atom of another comonomer; each Z¹⁰ and Z¹¹ independentlyrepresent a hydroxyl group, a C₁-C₄ alkoxy group, a C₁-C₄ alkyl group,or an oxygen atom bonded to a silicon atom of another monomer; and R isselected from the group consisting a C₁-C₈ alkylene group, a C₂-C₈alkenylene group, a C₂-C₈ alkynylene group, a nitrogen-containing C₁-C₁₀alkylene group, an optionally substituted C₆-C₂₀ aralkyl, and anoptionally substituted C₄-C₂₀ heterocycloalkyl group; (iv) anindependent cyclic polyurea monomer of Formula

 wherein each R¹ independently is a X¹OX²X³SiX⁴ group, wherein each X¹represents a hydrogen atom, a C₁-C₄ alkyl group or a bond to a siliconatom of another monomer unit; X² and X³ each independently represent ahydroxyl group, a C₁-C₄ alkyl group, a C₁-C₄ alkoxy group or an oxygenatom bonded to a silicon atom of another monomer unit; and each X⁴represents a C₁-C₈ alkylene group bonded to a nitrogen atom of thecyclic polyurea. (v) an independent unit of Formula M¹(OZ¹²)³ (VI),wherein M¹ represents a Group 13 metal and each Z¹² independentlyrepresents a hydrogen atom, a C₁-C₆ alkyl, or a bond to a silicon atomof another monomer; (vi) an independent unit of Formula(Z¹³O)₂M²-O—Si(OZ¹⁴)₃ (VII), wherein M² represents a Group 13 metal andZ¹³ and Z¹⁵ each independently represent a hydrogen atom, a C₁-C₆ alkylgroup, or a bond to a silicon atom of another monomer; and (vii) acombination thereof.
 30. The method of claim 29, wherein at least oneindependent unit of Formula (II) is present, wherein each Z³ representsa hydrogen atom, a C₁-C₂ alkyl group, or a bond to a silicon atom ofanother siloxane monomer; and each Z⁴ represents a C₁-C₂ alkyl group.31. The method of claim 30, wherein each Z³ represents a hydrogen atom,ethyl, or a bond to a silicon atom of another siloxane monomer; and eachZ⁴ represents methyl.
 32. The method of claim 29, wherein at least oneunit of Formula (III) is present, wherein each Z⁵ represents a hydrogenatom, a C₁-C₂ alkyl group, or a bond to a silicon atom of anothercomonomer; and Z⁶, Z⁷, and Z⁸ are each independently selected from thegroup consisting of a hydroxyl group, a C₁-C₂ alkyl group, C₁-C₂ alkoxygroup, a nitrogen-containing C₃-C₁₀ alkyl group, a nitrogen-containingC₄-C₁₀ heteroalkyl group, a nitrogen-containing optionally substitutedC₄-C₁₀ heterocycloalkyl group, and an oxygen atom bonded to a siliconatom of another monomer.
 33. The method of claim 32, wherein each Z⁵represents a hydrogen atom, methyl, ethyl, or a bond to a silicon atomof another comonomer; and Z⁶, Z⁷, and Z⁸ are each independently selectedfrom the group consisting of a hydroxyl group, methyl, methoxy, ethoxy,


34. The method of claim 29, wherein at least one independent unit ofFormula (IV) is present, wherein each Z⁹ represents a hydroxyl group, aC₁-C₂ alkoxy group, or an oxygen atom bonded to a silicon atom ofanother comonomer; each Z¹⁰ and Z¹¹ independently represent a hydroxylgroup, a C₁-C₂ alkoxy group, a C₁-C₂ alkyl group, or an oxygen atombonded to a silicon atom of another monomer; and R is selected from thegroup consisting of a C₁-C₄ alkylene group, a C₂-C₄ alkenylene group, aC₂-C₄ alkynylene group, a nitrogen-containing C₄-C₁₀ alkylene group, anoptionally substituted C₆-C₁₀ aralkyl and an optionally substitutedC₄-C₁₂ heterocycloalkyl group.
 35. The method of claim 34, wherein eachZ⁹ represents a hydroxyl group, methoxy, ethoxy, or an oxygen atombonded to a silicon atom of another comonomer; each Z¹⁰ and Z¹¹independently represent a hydroxyl group, methoxy, ethoxy, methyl, or anoxygen atom bonded to a silicon atom of another monomer; and R isselected from the group consisting of —CH₂—, —CH₂CH₂—, —HC═CH—,


36. The method of claim 29, wherein at least one independent unit ofFormula (V) is present, wherein each X¹ represents a hydrogen atom, aC₁-C₂ alkyl group, or a bond to a silicon atom of another monomer unit;X² and X³ each independently represent a hydroxyl group, a C₁-C₂ alkylgroup, a C₁-C₂ alkoxy group, or an oxygen atom bonded to a silicon atomof another monomer unit; and each X⁴ represents a C₁-C₄ alkylene groupbonded to a nitrogen atom of the cyclic compound.
 37. The method ofclaim 36, wherein each X¹ represents a hydrogen atom, methyl or a bondto a silicon atom of another monomer unit; X² and X³ each independentlyrepresent a hydroxyl group, methoxy or an oxygen atom bonded to asilicon atom of another monomer unit and each X⁴ represents —CH₂CH₂CH₂—bonded to a nitrogen atom of the cyclic polyurea.
 38. The method ofclaim 29, wherein at least one independent unit of Formula (VI) ispresent, wherein M¹ is Al or B and each Z¹² represents a hydrogen atom,a C₁-C₄ alkyl group, or a bond to a silicon atom or another monomer. 39.The method of claim 29, wherein at least one independent unit of Formula(VII) is present, wherein M² is Al or B and Z¹³ and Z¹⁴ eachindependently represent a hydrogen atom, a C₁-C₄ alkyl group, or a bondto a silicon atom of another monomer.
 40. The method of claim 26,wherein the organosilica material is made using substantially nostructure directing agent or porogen.
 41. The method of claim 26,wherein the another siliceous material is an amorphous silica.
 42. Themethod of claim 41, wherein the amorphous silica is a silica gel orMCM-41.
 43. An adsorbent material made by the method of claim
 20. 44. Amethod of separating a heteroatom species from a hydrocarbon feedstream,the method comprising contacting the hydrocarbon feedstream containingat least one heteroatom species with the adsorbent material of claim 1.45. The method of claim 44, wherein the heteroatom species is selectedfrom the group consisting of a nitrogen-containing species, asulfur-containing species, an oxygen-containing species, and acombination thereof.
 46. The method of claim 44, wherein the heteroatomspecies comprises nitrogen-containing species or sulfur-containingspecies.
 47. The method of claim 46, wherein at least about 20% of thenitrogen-containing species are separated from the hydrocarbonfeedstream.
 48. The method of claim 46, wherein at least about 10% ofthe sulfur-containing species are separated from the hydrocarbonfeedstream.
 49. The method of claim 44, wherein the hydrocarbonfeedstream is selected from the group consisting of whole crude, lightgas oil (LGO), light cycle oil (LCO), and virgin diesel.
 50. The methodof claim 44 further comprising hydrotreating the hydrocarbon feedstream.51. The method of claim 50, wherein hydrotreating is performed at ahydrogen pressure of about 200 psig to about 1600 psig.